[go: up one dir, main page]

CN101506946B - Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp - Google Patents

Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp Download PDF

Info

Publication number
CN101506946B
CN101506946B CN200780030345XA CN200780030345A CN101506946B CN 101506946 B CN101506946 B CN 101506946B CN 200780030345X A CN200780030345X A CN 200780030345XA CN 200780030345 A CN200780030345 A CN 200780030345A CN 101506946 B CN101506946 B CN 101506946B
Authority
CN
China
Prior art keywords
substrate
compound semiconductor
emitting device
iii nitride
iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200780030345XA
Other languages
Chinese (zh)
Other versions
CN101506946A (en
Inventor
三木久幸
塙健三
佐佐木保正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyoda Gosei Co Ltd
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006223261A external-priority patent/JP2008047763A/en
Priority claimed from JP2006291082A external-priority patent/JP2008106316A/en
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority claimed from PCT/JP2007/065902 external-priority patent/WO2008020599A1/en
Publication of CN101506946A publication Critical patent/CN101506946A/en
Application granted granted Critical
Publication of CN101506946B publication Critical patent/CN101506946B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors

Landscapes

  • Physical Vapour Deposition (AREA)
  • Led Devices (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Led Device Packages (AREA)
  • Semiconductor Lasers (AREA)

Abstract

Disclosed is a method for manufacturing a group III nitride compound semiconductor light-emitting device having excellent emission characteristics at high yield. Also disclosed are a group III nitride compound semiconductor light-emitting device and a lamp. Specifically disclosed is a method for manufacturing a group III nitride compound semiconductor light-emitting device, which comprises a step wherein a semiconductor layer composed of a group III nitride compound semiconductor containing Ga as a group III element is formed on a substrate (11) by sputtering. In this method, the substrate (11) and a sputtering target are arranged opposite to each other, and the distance between the substrate (11) and the sputtering target is set within the range of 20-100 mm. In addition, when the semiconductor layer is formed by sputtering, the bias value applied to the substrate (11) is set at 0.1 W/cm<2> or higher. Furthermore, when the semiconductor layer is formed, the sputtering is performed while supplying nitrogen and argon into a chamber which is used for the sputtering.

Description

The manufacturing approach of III group-III nitride compound semiconductor light-emitting device, III group-III nitride compound semiconductor light-emitting device and lamp
Technical field
The present invention relates to be applicable to the manufacturing approach of the III group-III nitride compound semiconductor light-emitting device of light-emitting diode (LED), laser diode (LD), electronic device etc., particularly relate to and to make the good III group-III nitride compound semiconductor crystallization of crystallinity on substrate, carry out manufacturing approach, III group-III nitride compound semiconductor light-emitting device and the lamp of epitaxially grown III group-III nitride compound semiconductor light-emitting device.
The application be based on August 18th, 2006 spy in japanese publication be willing to 2006-223260 number with special be willing to 2006-223261 number and on October 26th, 2006 spy in japanese publication be willing to require priority 2006-291082 number, its content is quoted in the application.
Background technology
III family (the 3rd main group) nitride semiconductor luminescent element has and is equivalent to by the band gap of visible light to the Direct Transfer type of the energy of the scope of ultraviolet region, and luminous efficiency is excellent, therefore can be used as the light-emitting component use of LED and LD etc.
In addition, when being used for electronic device, III group-III nitride semiconductor light-emitting component is compared during with the III-V compound semiconductor that uses in the past, can obtain having the electronic device of excellent specific property.
Such III group-III nitride compound semiconductor, usually with trimethyl gallium, triethyl-gallium and ammonia as raw material, adopt mocvd method to make.Mocvd method is to make the steam that contains raw material in the carrier gas and be transported to substrate surface, through decomposing with the reaction of heated substrate, thereby makes the method for crystalline growth.
In the past, as the single-crystal wafer of III-V compound semiconductor, on the single-crystal wafer of different materials, made crystalline growth and the method that obtains is common.Like this, at the variety classes substrate with carry out between the crystallization of epitaxially grown III group-III nitride semiconductor, there is bigger lattice unconformity (mismatch) above that.For example, at sapphire (Al 2O 3) when making gallium nitride (GaN) growth on the substrate, there is 16% lattice unconformity between the two, when on the SiC substrate, making the gallium nitride growth, between is deposited 6% lattice unconformity.
Usually, when the lattice unconformity that above-mentioned that kind is big exists, be difficult on substrate, make crystallization directly to carry out epitaxial growth, in addition, even there is the problem that can not obtain the good crystallization of crystallinity when growing.
Therefore following scheme was once proposed; Promptly; Utilize Metalorganic Chemical Vapor Deposition (MOCVD), when on sapphire single crystal substrate or SiC monocrystal substrate, making the crystallization of III group-III nitride semiconductor carry out epitaxial growth, the at first range upon range of layer that is called low temperature buffer layer that forms by aluminium nitride (AlN) or AlGaN on substrate; At high temperature make the crystallization of III group-III nitride semiconductor carry out epitaxially grown method more above that, this scheme is carried out (for example patent documentation 1,2) usually.
On the other hand, also studied through sputter and made the crystallization of III group-III nitride compound semiconductor, for example once proposed following scheme, that is, and through using the high frequency magnetron sputtering of nitrogen, at (100) face and the Al of Si 2O 3(0001) face on form the method (for example non-patent literature 1) of GaN film.In the method that non-patent literature 1 is put down in writing, as the condition of film forming, making total gas pressure is that 2mTorr, input electric power are 100W, and substrate temperature ℃ is changed in RT～900, in addition, as sputter equipment, makes the device of target and substrate subtend.
In addition, once propose following scheme, that is, make negative electrode and target relative, and between substrate and target, be added with the method (for example non-patent literature 2) of the device formation GaN film of screen cloth.In the method that non-patent literature 2 is put down in writing, as membrance casting condition, in nitrogen, making pressure is 0.67Pa, and making substrate temperature is 84～600 ℃, and input electric power is 150W, and the distance between substrate and the target is 80mm.
In addition, once proposed following scheme,, on substrate, formed the method (for example non-patent literature 3) of AlN film through making the target mode that is called faces cathode respect to one another.
In addition, once propose use DC magnetron sputtering method, on substrate, formed the method (for example non-patent literature 4) of AlN film.In the method that patent documentation 4 is put down in writing, make substrate and target subtend, at Ar and N 2Mixed-gas atmosphere in carry out sputter, as membrance casting condition, pressure is changed between 60～180mm in the distance of scope, substrate and the target of 0.2～0.8Pa.
In addition; Following scheme was once proposed; This scheme relates to layers such as forming AlN through the method beyond the MOCVD as resilient coating, adopts mocvd method to be formed on the method that resilient coating is attend the layer of institute's film forming again, for example through on the resilient coating of high-frequency sputtering film forming; Adopt the method (for example, patent documentation 3) of the crystallization of mocvd method growth phase composition together.But in the method that patent documentation 3 is put down in writing, existence can not stably obtain the problem (with reference to patent documentation 4,5) of good crystallization.
Therefore,, once proposed following scheme, for example, comprising the method (for example, patent documentation 4) of annealing in the mist of ammonia and hydrogen after the buffer growth in order stably to obtain good crystallization; With the method (for example, patent documentation 5) of under the temperature more than 400 ℃, passing through DC sputter formation resilient coating.
In addition; In the method that patent documentation 4 and 5 is put down in writing; As baseplate material, can use sapphire, silicon, carborundum, zinc oxide, gallium phosphide, GaAs, magnesia, manganese oxide, III group-III nitride based compound semiconductor monocrystalline etc., wherein preferred sapphire a face substrate.
Patent documentation 1: No. 3026087 communique of Japan Patent
Patent documentation 2: japanese kokai publication hei 4-297023 communique
Patent documentation 3: the special fair 5-86646 communique of Japan
Patent documentation 4: No. 3440873 communique of Japan Patent
Patent documentation 5: No. 3700492 communique of Japan Patent
Non-patent literature 1: ox nine BUGY CRAXONE (Y.USHIKU) etc., " 21 century associating Conference Papers collection ", Vol.2nd, p295 (2003)
Non-patent literature 2: テ イ one キ Network マ (T.Kikuma) etc., " vacuum (Vacuum) ", Vol.66, P233 (2002)
Non-patent literature 3: キ Network オ ト ミ Na ガ (Kikuo Tominaga) etc., " Japanese applicating physical magazine (Japanese Journal of Applied Physics) ", Vol.28, p7 (1989)
Non-patent literature 4: エ system イ シ Ha ラ (M.Ishihara) etc., " thin solid film (ThinSolid Films) ", Vol.316, p152 (1998)
Summary of the invention
But; The result that the applicant etc. carry out deep experiment, research finds; Even when carrying out film forming, can not stably obtain containing the III group-III nitride compound semiconductor of Ga as III family element with good crystallization according to the condition of record in patent documentation 4 and the patent documentation 5.That is, in the method that patent documentation 4,5 is put down in writing, on the resilient coating that adopts sputtering film-forming, adopt mocvd method to form the GaN layer.When adopting sputtering method to form resilient coating, film forming speed is fast, but according to membrance casting condition, becomes the resilient coating of crystallinity difference sometimes.When on the low resilient coating of such crystallinity, when adopting mocvd method to make the GaN layer growth, worry that the crystallinity of GaN layer significantly reduces.
In addition, use the condition of non-patent literature 1,2 records, when adopting sputtering method to form the GaN layer, also have the problem that is difficult on resilient coating, form the good GaN layer of crystallinity.
The present invention accomplishes in view of above-mentioned problem; Its purpose is to provide can stablize and form with the short time crystalline film that is formed by III group-III nitride compound semiconductor have good uniformity; When productivity ratio is excellent, have manufacturing approach, III group-III nitride compound semiconductor light-emitting device and the lamp of the III group-III nitride compound semiconductor light-emitting device of the excellent characteristics of luminescence.
The result that the inventor furthers investigate in order to address the above problem has accomplished the present invention.That is, the present invention relates to following scheme.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; In with said substrate and the configuration of sputtering target subtend ground, make the scope that is spaced apart 20～100mm of said substrate and said sputtering target.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; When forming said semiconductor layer, the power that puts on sputtering target applies through high-frequency mode or pulsed D C mode.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; When forming said semiconductor layer, making the indoor vacuum degree of in sputter, using in advance is 1.0 * 10 -3After below the Pa, to said indoor base feed.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that the position relation that makes said substrate and sputtering target is for facing formula.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; When forming said semiconductor layer, make the magnetic field rotation or make magnetic field shake (swing) with respect to sputtering target.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[5] is characterized in that, forms said semiconductor layer through the reactive sputtering method that the nitride raw material is circulated in reactor.
Manufacturing approach according to [6] described III group-III nitride compound semiconductor light-emitting device is characterized in that, uses nitrogen as said nitride raw material.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[7] is characterized in that, between said substrate and said semiconductor layer, forms the resilient coating that comprises column crystallization.
Manufacturing approach according to [8] described III group-III nitride compound semiconductor light-emitting device is characterized in that, adopts sputtering method to form said resilient coating.
Manufacturing approach according to [8] or [9] described III group-III nitride compound semiconductor light-emitting device is characterized in that, forms said resilient coating by the III group-III nitride compound that contains as the Al of III family element.
Manufacturing approach according to [10] described III group-III nitride compound semiconductor light-emitting device is characterized in that, forms said resilient coating by AlN.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [8]～[11] is characterized in that, forms said resilient coating with the mode more than at least 90% on the surface that covers said substrate.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [8]～[12] is characterized in that the width that constitutes the column crystallization of said resilient coating is the scope of 0.1～100nm.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [8]～[13] is characterized in that the thickness of said resilient coating is the scope of 10～500nm.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [8]～[14] is characterized in that, when forming said resilient coating by AlN, is formed the said semiconductor layer that is formed by III group-III nitride compound by GaN.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[15] is characterized in that, said substrate uses sapphire.
A kind of III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacturing approach of above-mentioned [1]～[16] to obtain.
A kind of lamp, it has used above-mentioned 17 described III group-III nitride compound semiconductor light-emitting devices.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; When adopting sputtering method to form said semiconductor layer, make bias voltage (bias) value that puts on said substrate be 0.1W/cm 2More than.
A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; When adopting sputtering method to form said semiconductor layer, making the power that puts on sputtering target is 0.1W/cm 2～100W/cm 2Scope.
Manufacturing approach according to [19] or [20] described III group-III nitride compound semiconductor light-emitting device is characterized in that, forms said semiconductor layer through the reactive sputtering method that the nitride raw material is circulated in reactor.
Manufacturing approach according to [21] described III group-III nitride compound semiconductor light-emitting device is characterized in that, has used nitrogen as said nitride raw material.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [19]～[22] is characterized in that, between said substrate and said semiconductor layer, forms the resilient coating that comprises column crystallization.
Manufacturing approach according to [23] described III group-III nitride compound semiconductor light-emitting device is characterized in that, adopts sputtering method to form said resilient coating.
Manufacturing approach according to [24] described III group-III nitride compound semiconductor light-emitting device is characterized in that, forms said resilient coating by the III group-III nitride compound that contains Al.
Manufacturing approach according to [25] described III group-III nitride compound semiconductor light-emitting device is characterized in that, forms said resilient coating by AlN.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [23]～[26] is characterized in that, forms said resilient coating with the mode more than at least 90% on the surface that covers said substrate.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [23]～[27] is characterized in that the width that constitutes the column crystallization of said resilient coating is the scope of 0.1～100nm.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [23]～[28] is characterized in that the thickness of said resilient coating is the scope of 10～500nm.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [23]～[29] is characterized in that, when forming said resilient coating by AlN, is formed the said semiconductor layer that is formed by III group-III nitride compound by GaN.
Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [19]～[30] is characterized in that, said substrate uses sapphire.
A kind of III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacturing approach of above-mentioned [19]～[31] to obtain.
A kind of lamp, it has used above-mentioned [32] described III group-III nitride compound semiconductor light-emitting device.
The invention effect
According to the manufacturing approach of III group-III nitride compound semiconductor light-emitting device of the present invention,, can adopt sputtering method to form the crystalline film that has good uniformity with the short time through above-mentioned formation.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.Therefore, can obtain the III group-III nitride compound semiconductor light-emitting device that productivity ratio is excellent and have the excellent characteristics of luminescence.
Description of drawings
Fig. 1 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the cross section structure of expression laminated semiconductor.
Fig. 2 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of expression planar structure.
Fig. 3 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of expression cross section structure.
Fig. 4 is the lamp that the explanation of pattern ground uses III group-III nitride compound semiconductor light-emitting device of the present invention to constitute.
Fig. 5 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is transmission electron microscope (TEM) photo of expression cross section structure.
Fig. 6 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is that TEM photo shown in Figure 5 is carried out the figure that medelling is represented.
Fig. 7 is the figure of an example of the manufacturing approach of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the structure of the rock type sputter equipment of expression.
Fig. 8 is the figure of an example of the manufacturing approach of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the structure of the revolving sputter equipment of expression.
Description of reference numerals
1...III group-III nitride compound semiconductor light-emitting device
10... laminated semiconductor
11... substrate
11a... surface
12... resilient coating
13... basalis
14...n type semiconductor layer
15... luminescent layer
16...p type semiconductor layer
17... light transmission is anodal
3... lamp
Embodiment
(first execution mode)
Below, the execution mode for manufacturing approach, III group-III nitride compound semiconductor light-emitting device and the lamp of III group-III nitride compound semiconductor light-emitting device of the present invention suitably describes with reference to Fig. 1～7.
The III group-III nitride compound semiconductor light-emitting device of this execution mode (below; Sometimes abbreviate light-emitting component as) manufacturing approach; Being on substrate, to use sputtering method to form the method for the semiconductor layer that is formed by III group-III nitride compound semiconductor at least, is the method for using the compound that contains Ga as III group-III nitride compound semiconductor.
Use the illustrative laminated semiconductor 10 of Fig. 1, the laminated construction of the light-emitting component that the manufacturing approach through this execution mode obtains is described.This laminated semiconductor 10 has the resilient coating 12 that is formed by III group-III nitride compound in substrate 11 laminated, on this resilient coating 12, is formed with and stacks gradually the semiconductor layer 20 that n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16 form.
Then; The laminated semiconductor 10 of this execution mode; Example as Fig. 2 and Fig. 3 represent is such, at p type semiconductor layer 16 laminated light transmissions positive pole 17, when forming positive terminal pad 18 more above that; At the regional 14d laminated negative pole 19 that exposes that is formed on the n type contact layer 14b of n type semiconductor layer 14, thereby can constitute light-emitting component 1.
[using the film forming of the semiconductor layer of sputtering method]
The manufacturing approach of light-emitting component of the present invention; As above-mentioned; Be to use sputtering method on substrate 11, to form the method for the layer of formation semiconductor layer 20 at least, in this execution mode, adopt: the employing sputtering method forms the basalis 14a of the n type semiconductor layer 14 among the formation semiconductor layer 20 and the method for n type contact layer 14b.
In order to use sputtering method on substrate, to form the excellent III group-III nitride compound semiconductor layer of crystallinity, must generate the higher reactive material of energy, make the migration (migration) on the substrate active, in this execution mode the method for following detailed description therefore.
As the sputtering method that in the manufacturing approach of this execution mode, uses, preferably, sputtering target is applied power through using RF (high frequency) sputtering method or DC sputtering method.
In addition, during the reactive sputtering method usually after use, stated,, more preferably use the RF sputtering method from easily controlling the viewpoint of film forming speed.
In addition, in the DC sputtering method, when using the reactive sputtering method, if apply the state of electric field continuously with DC, then sputtering target charging is difficult to improve film forming speed, therefore gives the pulsed DC sputtering method of bias voltage with being preferably pulse feature.
In addition; When adopting sputtering method to form semiconductor layer, carry out the method for film forming through the reactive sputtering method that the nitride raw material is circulated in reactor, can keep crystallinity well through the control reaction; Can stably reproduce its good crystallinity, thereby more preferably.
In addition, in this execution mode, when adopting sputtering method to form semiconductor layer, preferably make the magnetic field rotation or magnetic field is shaken with respect to metallic target 47.
Particularly when using the RF sputter, as the method for avoiding charging, preferred on one side with the position of magnet at target (sputtering target) Yi Bian in the mobile film forming of carrying out.
The movement technique of concrete magnet can suitably be selected according to the kind of sputter equipment, for example, magnet is shaken or rotatablely moves.
In the illustrative sputter equipment 40 of Fig. 7, dispose magnet 42 in the below (below of Fig. 7) of metallic target (sputtering target) 47, this magnet 42, shakes along target platform 43 below metallic target 47 through omitting illustrated drive unit.In chamber 41, supply with nitrogen and argon gas, on the substrate that is installed on heater 44 11, adopt sputtering method to form semiconductor layer.
In addition, in the illustrative sputter equipment 50 of Fig. 8, below metallic target 47 (below of Fig. 8); Dispose oval-shaped magnet 52; This magnet 52 is rotating shaft with the central shaft 53a of the target platform 53 of the circle of having accommodated metallic target 47, below metallic target 47, is rotated (the arrow R direction of Fig. 8).
At this moment, magnet 52, rotation below metallic target 47 under the state of the plasma circle being lived by the magnetic field that utilizes this magnet 52 to produce, so plasma becomes the shape around metallic target 47 surfaces, can have the ground of omission and uses metallic target 47.Therefore in addition, can prevent that metallic target 47 surfaces from being covered by product, have from metal forming 47 to substrate 11, be attached to the effect of substrate 11 efficiently from all directions sputtering particle that disperses.
In this execution mode,, can enumerate pressure, nitrogen partial pressure, film forming speed, substrate temperature and bias voltage etc. in the stove as the important parameters in the film forming of using sputtering method.
In the manufacturing approach of this execution mode, when forming semiconductor layer 20, preferably making the chamber 41 interior vacuum degrees of sputter equipment 40 in advance is 1.0 * 10 -3After below the Pa, base feed carries out film forming in chamber 41.
Vacuum degree through in the chamber 41 that makes above-mentioned sputter equipment 40 is above-mentioned scope, becomes low pressure in the chamber 41, becomes the state that has reduced the impurity in the chamber 41.Under this state in chamber 41 base feed, carry out the film forming of semiconductor layer 20, can not sneak into impurity thus, can obtain the good semiconductor layer of crystallinity 20.
Pressure in the chamber 41 when in addition, adopting sputtering method to form semiconductor layer 20 is preferably more than the 0.3Pa.Pressure in the chamber 41 is during less than 0.3Pa, and the amount of nitrogen becomes too small, worries to be attached on the substrate 11 with the state that does not become nitride by the metal of sputter.In addition, the upper pressure limit in the chamber 41 is not special to be limited, but need be suppressed to the pressure of the degree that can produce plasma.
In addition, the nitrogen flow is with respect to nitrogen (N 2) and the ratio of the flow of Ar, preferred N 2It is 20%～98% scope.When being lower than the flow-rate ratio of this scope, splash-proofing sputtering metal is attached on the substrate with metallic state.In addition, when being when being higher than the flow-rate ratio of above-mentioned scope, because the amount of Ar is very few, so sputtering rate is low.
The nitrogen flow is with respect to nitrogen (N 2) and the ratio of the flow of Ar, be preferably 25%～90% scope especially.
In the manufacturing approach of this execution mode, as above-mentioned, make the nitrogen concentration in the indoor gas of sputter equipment high, and then, mix Ar with above-mentioned flow-rate ratio as the big gas of weight.When indoor gas only is nitrogen,, therefore limited film forming speed, in this execution mode,, when can improving film forming speed, made the migration on the substrate 11 active through mixing with the big Ar of above-mentioned flow-rate ratio and weight owing to knock a little less than the power of metallic target 47.
As the nitrogen raw material that in this execution mode, uses, can have no restrictedly and to use known nitrogen compound usually, but ammonia, nitrogen (N2) is because simple to operate and can obtain more cheaply, thereby preferred.
The decomposition efficiency of ammonia is good, can carry out film forming with the high speed of growth, but because reactive, toxicity is high, therefore need remove the evil equipment and detector in addition, must make the material of the member that uses in the reaction unit be the high material of chemical stability.
In addition, using nitrogen (N 2) during as raw material, as device can be easy to use device, but can not obtain high reaction speed.But, if,, therefore consider and take into account the nitrogenous source that is best suited for installation cost though then can obtain the film forming speed of the available degree on commercial production of hanging down than ammonia for through importing to the method in the device after the decompose nitrogen such as electric field, heat.
Film forming speed when using the film forming of sputtering method is preferably the scope of second 0.01nm/ second～10nm/.During second, film-forming process is long-time to film forming speed less than 0.01nm/, and waste is big on commercial production.Film forming speed during second, is difficult to obtain good film greater than 10nm/.
In the manufacturing approach of this execution mode, use sputtering method form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the semiconductor layer 20 at least, therefore film forming speed can be improved, and film forming (manufacturing) time can be shortened.Through shortening manufacturing time, can suppress impurity and get into indoor in the sputter equipment to Min..
Substrate 11 preferably carries out the pre-treatment of wet type.For example, for the substrate of being processed by silicon 11, carry out RCA washing methods that people know etc., make the surface be the hydrogen terminal, film-forming process is stable thus.
In addition, substrate 11 in importing reactor the back, form before the resilient coating 12, can use the method for sputtering method etc. to carry out pre-treatment.Specifically, can be through substrate 11 be exposed to Ar, N 2Plasma in put the surface in order.For example, through making Ar gas, N 2The action of plasma of gas etc. can be removed the organic substance and the oxide that are attached to substrate 11 surfaces in substrate 11 surfaces.Under this situation, if between substrate 11 and chamber, apply voltage, then plasma particle acts on substrate 11 efficiently.
The inventor etc. carry out the result of deep experiment, research, and the temperature of the substrate 11 during film forming is preferably the scope of room temperature～1200 ℃, and more preferably 300 ℃～1000 ℃ scope most preferably is 500 ℃～800 ℃ scope.
The temperature of substrate 11 is prescribed a time limit down less than above-mentioned, has suppressed the migration on the substrate 11, and can not make the good III group-III nitride compound semiconductor crystalline film of crystallinity.The temperature of substrate 11 surpasses above-mentioned going up in limited time, worries III group-III nitride compound semiconductor crystallization decomposition.
In addition, the room temperature of explanation in the present invention is the temperature of the environment that also has influence on operation etc., but as concrete temperature, is 0～30 ℃ scope.
In the manufacturing approach of this execution mode, making the temperature of the substrate 11 when adopting sputtering film-forming is above-mentioned scope, and substrate temperature is improved, and can make the motion activation of the reactive material (from the metal of metallic target 47 taking-ups) of arrival substrate 11 at crystal surface thus.
When using sputtering method to form mixed crystal, the method that the metal that becomes target is prepared as the mixture (can form alloy) of metal material is in advance arranged, can also be two targets preparing to constitute by material different, and the method for side by side carrying out sputter.
For example, when forming the film of definite composition, can use the target of composite material, when several kinds of different films are formed in formation, can be arranged at a plurality of targets indoor.
In the manufacturing approach of this execution mode, in substrate 11 and the configuration of metallic target (sputtering target) 47 subtends ground, the interval of substrate 11 and metallic target 47 is preferably the scope of 20～100mm, the more preferably scope of 30～50mm.
Interval through making substrate 11 and metallic target 47 can be supplied with the reactive material of higher energy to substrate 11 in above-mentioned scope, and the migration on the substrate comes to life, and can form the excellent III group-III nitride compound semiconductor layer of crystallinity.
In the manufacturing approach of this execution mode, the position relation that preferably makes substrate 11 and metallic target 47 is for facing formula.
As above-mentioned, in the chamber 41 of sputter equipment 40, substrate 11 is disposed at the formation in the plasma through becoming, higher energy is supplied to substrate 11, so the migration on the substrate 11 comes to life, and the cyclisation of dislocation is carried out easily.
Thus, can form the excellent III group-III nitride compound semiconductor layer of crystallinity.
In the manufacturing approach of this execution mode; Through under these conditions, use sputtering method to form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the semiconductor layer 20 at least, can generate high bias voltage or high-power reactive material; In addition; Can this reactive material be supplied with to substrate 11 with high kinergety, therefore on substrate 11, produce migration, make the dislocation cyclisation easily.Thus, constitute the basalis 14a of the n type semiconductor layer 14 of semiconductor layer 20, the crystallinity as the resilient coating 12 of the aggregate of the column crystallization of film forming on substrate 11 is not inherited on former state ground.Therefore, can be formed into membrane efficiency height, productivity ratio excellence, and the excellent III group-III nitride compound semiconductor of crystallinity.
[laminated construction of light-emitting component]
Below detail for the formation of the light-emitting component 1 that obtains through this execution mode manufacturing approach of on substrate 11, using sputtering method to form semiconductor layer 20 at least as stated.
<substrate >
In this execution mode, as the material that can be used for substrate 11, so long as can make the crystallization of III group-III nitride compound semiconductor carry out epitaxially grown baseplate material on the surface, just not special the qualification can select various materials to use.For example, can enumerate sapphire, SiC, silicon, zinc oxide, magnesia, manganese oxide, zirconia, manganese oxide zinc-iron, oxidation magnalium, zirconium boride, gallium oxide, indium oxide, lithia gallium, lithia aluminium, neodymia gallium, lanthana strontium aluminium tantalum, strontium oxide strontia titanium, titanium oxide, hafnium, tungsten, molybdenum etc.
In addition; Do not use ammonia and form resilient coating; And the basalis of the n type semiconductor layer that method that adopt to use ammonia is stated after forming and constituting, and, use in the aforesaid substrate material known through at high temperature contacting the occasion of oxide substrate that ammonia causes chemical modification, metal substrate etc.; The resilient coating of this execution mode plays a role as coating, is being effective aspect the chemical modification that prevents substrate therefore.
In addition, the temperature that common sputtering method can suppress substrate makes it lower, even therefore use the occasion of the substrate of being processed by the material with the character of at high temperature decomposing, also can not cause damage to substrate 11, and can on substrate, carry out the film forming of each layer.
< resilient coating >
The laminated semiconductor 10 of this execution mode adopts sputtering method on substrate 11, to be formed with the resilient coating 12 that is formed by III group-III nitride compound.Through sputtering method, for example, through raw metal and the gas that comprises V group element by plasma-activated, react, can form resilient coating 12.
For the laminated semiconductor 10 of the III group-III nitride compound semiconductor light-emitting device 1 of this execution mode; When on substrate 11, making the crystallization of III group-III nitride compound semiconductor carry out epitaxial growth; Can form the resilient coating 12 that the aggregate by column crystallization constitutes through the sputtering method that utilizes plasma to carry out activation III family raw metal and the gas that comprises the nitrogen element, and adopt sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14 above that.
The crystallization of III group-III nitride compound semiconductor has the crystalline texture of hexagonal crystal system, and forming with six prisms easily is basic set tissue.Particularly through use the plasma change the film that forms of the film build method of metal material, become column crystallization easily.At this, the column crystallization of explaining among the present invention is meant forming crystal boundary with adjacent intergranule and separating, and self is the crystallization of column as vertical sectional shape.
Transmission electron microscope (TEM) photo in the cross section of the III group-III nitride compound semiconductor laminated structure among the embodiment 1 that Fig. 5 states after being, Fig. 6 is the figure with Fig. 5 medelling.Resilient coating 12 is separated by the border of representing with solid line among Fig. 6, and each ingot between border and border is the shape of hexagonal post.In the present invention, the aggregate that such crystal habit is called column crystallization.In addition, as being distinguished by Fig. 5 and Fig. 6, such crystal habit also can be called the layer of being separated by the border, but in the present invention, also comprises such layer interior, describes as the aggregate of column crystallization.
Under the situation on the substrate 11, the semiconductor layer that is formed by III group-III nitride compound semiconductor of film forming becomes the crystalline film with well-crystallized property above that in the resilient coating that comprises such column crystallization 12 film forming.
Resilient coating 12 must covered substrate 11 more than at least 60% of surperficial 11a, preferably cover more than 80%, preferably form with the mode that covers more than 90%.
In addition, resilient coating 12 most preferably with 100% the mode of covering surfaces 11a, promptly forms with the mode on the surperficial 11a of ground very close to each other covered substrate 11.
When the zone of the surperficial 11a of resilient coating 12 covered substrates 11 diminishes; Become the state that expose significantly on surface 11; With directly its lattice constant of basalis 14a of film forming is different on substrate 11, therefore do not become uniform crystallization at the basalis 14a of film forming on the resilient coating 12, produce hillock or hole.
In addition, the ratio of the surperficial 11a of resilient coating 12 covered substrates 11 can be measured through cross section TEM photo as shown in Figure 5.Particularly the material of resilient coating 12 and basalis 14a not simultaneously, the surface through using EDS etc. and substrate 11 is the interface of the layer on scanning substrate 11 and this substrate 11 abreast, can estimate the ratio in the zone that does not form resilient coating 12.
In addition, in this execution mode, as above-mentioned, measure the area that substrate 11 exposes, but prepare only to have formed the sample of resilient coating 12, also can measure the area that substrate 11 exposes through methods such as AFM according to cross section TEM photo.
In addition, when on substrate 11, forming resilient coating 12, as the example that Fig. 1 representes, can form, also can form with the surperficial 11a of covered substrate 11 and the mode of side with the mode of the surperficial 11a of covered substrate 11 only.In addition, also can form with the mode at surperficial 11a, side and the back side of covered substrate 11.
Consider that from the buffering function aspects preferred resilient coating 12 is made up of the aggregate of column crystallization.
The crystallization of III group-III nitride compound semiconductor has the crystalline texture of hexagonal crystal system, and forming with six prisms easily is basic set tissue.Particularly, through use the plasma change the film that forms of the film build method of metal material, become column crystallization easily.
On substrate 11, form like this when comprising the resilient coating 12 of column crystallization, the pooling feature of resilient coating 12 effectively plays a role, and therefore the III group-III nitride compound semiconductor of film forming becomes and has good crystalline crystalline film above that.
In addition, from the aspect of buffering function, in the resilient coating 12, the mean value of the width of each crystal grain of above-mentioned column crystallization is preferably the scope of 0.1～100nm, more preferably the scope of 1～70nm.
Good for the crystallinity of the crystallizing layer that makes III group-III nitride compound semiconductor, suitably the width of each crystal grain of control column crystallization specifically, is preferably above-mentioned scope.
The width of the crystal grain of each column crystallization can easily be measured through cross section tem observation etc.That is the width of the crystal grain that is spaced apart each column crystallization on the border of each column crystallization in the ideograph represented of Fig. 6.In addition, as the TEM photo of being represented by Fig. 5 was also distinguished, the width of each column crystallization can not critically stipulate to have the distribution of width to a certain degree.Thereby the width of the crystal grain of each column crystallization has about for example several percentages even break away from the crystallization of above-mentioned scope, also can not influence effect of the present invention.In addition, the width of the crystal grain of each column crystallization preferably has more than 90% in above-mentioned scope.
The crystal grain of crystallization, the preferred roughly shape of column that is as above-mentioned, resilient coating 12, the crystal grain of preferred column is gathered and cambium layer.
At this, the width of above-mentioned crystal grain when resilient coating 12 is the aggregate of columnar grain, is meant the distance at the interface and the interface of crystallization.On the other hand, when crystal grain disperseed to exist with island, the width of crystallization was meant the catercorner length of the best part of the face that crystallization crystal grain contacts with real estate.
The thickness of resilient coating 12 is preferably the scope of 10～500nm, more preferably the scope of 20～100nm.
The thickness of resilient coating 12 is during less than 10nm, and the pooling feature as above-mentioned is insufficient.In addition, when forming resilient coating 12 with the thickness that surpasses 500nm, although do not change as the function of coating, the film forming processing time is elongated, worries that productivity ratio reduces.
In addition, about the bed thickness of resilient coating 12,, can easily measure according to above-mentioned cross section TEM photo.
Resilient coating 12 is preferably the composition that contains Al, is preferably especially by what AlN formed to constitute.
In addition, as the material that constitutes resilient coating 12, so long as the III group-III nitride compound semiconductor of being represented by general formula AlGaInN then can use any material.And then, also can be for containing as the As of V family, the formation of P.
Making resilient coating 12 is when containing the composition of Al, wherein to be preferably GaAlN, and at this moment, the composition of Al is preferably more than 50%.
In addition, resilient coating 12 through for to be made up of what AlN formed, can become the column crystallization aggregate efficiently, thereby more preferably.
In addition, as above-mentioned, resilient coating 12 can form with the mode that except the surperficial 11a of covered substrate 11, also covers side 11b.And then, also can form with the mode of the back side 11c that goes back covered substrate 11.Yet, when the film build method formation resilient coating that adopts in the past, need carry out maximum about 6 times～8 times film forming and handle, become long operation.As the film build method beyond this, also can consider through substrate is not kept being arranged at indoorly, carry out the method for film forming at substrate on comprehensively, but needing the occasion of heated substrates, worry that device becomes complicated.
Therefore, for example can consider on one side through substrate being shaken or rotatablely move, and make of the sputter direction change of the position of substrate, Yi Bian carry out the method for film forming with respect to filmogen.Through adopting such method, operation that can be through once then, through carrying out the film formation process to substrate back, can adopt the surface and the side film forming of substrate to add up to twice operation covered substrate comprehensive.
In addition, also can be: the filmogen source constitutes for what produced by large-area generation source, and through the occurrence positions of mobile material, moving substrate does not just carry out the method for film forming comprehensively at substrate.As such method, as above-mentioned, can enumerate out on one side through magnet being shaken or rotatablely move, on one side and the RF sputtering method of film forming carries out in the position of the magnet of swap cathode in target.In addition, when carrying out film forming, also can be the method that substrate-side and cathode side are moved through such RF sputtering method.And then; If through will be near substrate as the cathode arrangement in the generation source of material; Make and not supply with the plasma that takes place to substrate, but become the formation of supplying with the mode that substrate is wrapped into that then film forming becomes possibility substrate surface and side the time with pencil.
< semiconductor layer >
That kind as shown in Figure 1; The laminated semiconductor 10 of this execution mode; On substrate 11, being situated between has the resilient coating 12 of above-mentioned that kind and range upon range of semiconductor layer 20 is arranged, said semiconductor layer 20 have form by nitride-based compound semiconductor, n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16.
In addition, in n type semiconductor layer 14, have and adopt basalis 14a and n type contact layer 14b sputtering film-forming, that formed by III group-III nitride compound semiconductor at least, on resilient coating 12, range upon range of have a basalis 14a.
Can form following formation: on the basalis 14a that is formed by III group-III nitride compound semiconductor, as above-mentioned, range upon range of laminated semiconductor shown in Figure 1 10 is such has functional crystallizing layer.For example, when being formed for the semiconductor laminated structure of light-emitting component, p type conductive layer of the p type alloy of the n type conductive layer of the n type alloy of can range upon range ofly mix Si, Ge, Sn etc., the magnesium that mixed etc. etc. and forming.In addition,, in luminescent layer etc., InGaN can be used, in coating etc., AlGaN can be used as material.Like this, through on basalis 14a, further forming III group-III nitride compound semiconductor crystallizing layer, can make wafer making, that have semiconductor laminated structure that is used for light-emitting diode, laser diode or electronic device etc. with function.
Below, laminated semiconductor 10 is detailed.
As nitride-based compound semiconductor, known a plurality of for example by general formula Al XGa YIn ZN 1-AM A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0≤A＜1.) gallium nitride compound semiconductor of expression, in the present invention, also can have no restrictedly use comprise gallium nitride compound semiconductor that these are known, by general formula Al XGa YIn ZN 1-AM A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0≤A＜1.) expression gallium nitride compound semiconductor.
Gallium nitride compound semiconductor except Al, Ga and also can contain other III family element the In, also can contain the element of Ge, Si, Mg, Ca, Zn, Be, P, As and B etc. as required.And then, be not limited to the element that have a mind to add, also comprise the trace impurity that contains in the impurity that exists with ... membrance casting condition and must contain and raw material, the reaction tube material sometimes.
The growing method of these gallium nitride compound semiconductors is not special to be limited; Except above-mentioned sputtering method, the known whole method that makes nitride semiconductor growing of also applicable MOCVD (Metalorganic Chemical Vapor Deposition), HVPE (hydride vapor growth method), MBE (molecular beam epitaxy) etc.As preferred growing method,, be mocvd method from the viewpoint of film thickness monitoring property, production.In mocvd method, can use hydrogen (H as carrier gas 2) or nitrogen (N 2); Can use trimethyl gallium (TMG) or triethyl-gallium (TEG) as the Ga source of III family raw material, can use trimethyl aluminium (TMA) or triethyl aluminum (TEA), can use trimethyl indium (TMI) or triethylindium (TEI) as the In source as the Al source; As the nitrogenous source of V family raw material, can use ammonia (NH 3), hydrazine (N 2H 4) etc.In addition, as alloy, in the n type, can use monosilane (SiH as the Si raw material 4) or disilane (Si 2H 6), can use germane gas (GeH as the Ge raw material 4), tetramethyl germanium ((CH 3) 4Ge), tetraethyl germanium ((C 2H 5) 4Ge) etc. organic germanium compounds.In the MBE method, the germanium of element state also can be used as doped source and uses.In the p type, for example use bis-cyclopentadienyl magnesium (Cp as the Mg raw material 2Mg) or two ethyl cyclopentadienyl group magnesium (EtCp 2Mg).
[n type semiconductor layer]
N type semiconductor layer 14 is laminated on the above-mentioned resilient coating 12 usually, is made up of basalis 14a, n type contact layer 14b and n type coating 14c.In addition, but n type contact layer double as is basalis and/or n type coating.
(basalis)
The basalis 14a of this execution mode is formed by III group-III nitride compound semiconductor, can through aforesaid sputtering method on resilient coating 12 laminated ground film forming.
As the material of basalis 14a, may not be identical with the resilient coating 12 of film forming on substrate 11, also can use material different, preferably by Al xGa 1-xN layer (0≤x≤1 is preferably 0≤x≤0.5, further is preferably 0≤x≤0.1) constitutes.
The result that the inventor etc. experimentize is clear and definite, as the material that in basalis 14a, uses, preferably contain Ga III group-III nitride compound, be the GaN based compound semiconductor.
Above-mentioned resilient coating 12 for forms by AlN constitute the time, basalis 14a must make the dislocation cyclisation through migration, so that the succession of former state ground is not as the crystallinity of the resilient coating 12 of the aggregate of column crystallization.As the material of the cyclisation that is easy to generate dislocation, can enumerate the GaN based compound semiconductor that comprises Ga, preferred especially AlGaN or GaN.
The thickness of basalis 14a is preferably more than the 0.1 μ m, more preferably more than the 0.5 μ m, most preferably is more than the 1 μ m.When this thickness is above, obtain the good Al of crystallinity easily xGa 1-xThe N layer.
In basalis 14a, as required, can mix 1 * 10 17～1 * 10 19/ cm 3Scope in n type impurity, but also can undope (＜1 * 10 17/ cm 3), consider from keeping good crystalline aspect, preferably undope.
When substrate 11 is conductivity, form conductivity through doping alloy in basalis 14a, can be at the electrode of formation up and down of light-emitting component.On the other hand, when in basic 11, using the material of insulating properties, become the chip structure that identical faces at light-emitting component is provided with each electrode of anodal and negative pole, so basalis 14a need not mix, crystallinity becomes good thereby preferably when undoping.
As n type impurity, not special the qualification can be enumerated for example Si, Ge and Sn etc., preferably enumerates Si and Ge.
When in substrate 11, using the substrate of conductivity, as above-mentioned, 14a mixes to basalis, and the layer structure that makes basalis 14a can form the structure that electrode is set on the chip two sides of light-emitting component in the longitudinal stream overcurrent.
In addition, when in substrate 11, using the insulating properties substrate, be employed in the chip structure of identical surface forming electrode of the chip of light-emitting component, therefore on substrate 11, be situated between resilient coating 12 is arranged and range upon range of basalis 14a when not have the crystallization of doping, it is good that crystallinity becomes.
When adopting sputtering method to form basalis 14a, come the method for film forming in reactor, can keep crystallinity well, can stably reproduce this good crystallinity through the control reaction through the reactive sputtering method that the nitride raw material is circulated, thereby more preferably.
In addition, when adopting sputtering method to form basalis 14a, compare, can make device become easy formation with mocvd method, MBE method etc.
The temperature of the substrate 11 when forming basalis 14a, promptly the growth temperature of basalis 14a is preferably the temperature more than 800 ℃.This is because pass through to improve the temperature of the substrate 11 when forming basalis 14a, is easy to generate the migration of atom, and the cyclisation of dislocation is carried out easily.In addition, the temperature of the substrate 11 when forming basalis 14a is necessary for the low temperature of temperature of decomposing than crystallization, therefore is preferably less than 1200 ℃.If the temperature of the substrate 11 when forming basalis 14a then can obtain the good basalis 14a of crystallinity in the said temperature scope.
(n type contact layer)
The n type contact layer 14b of this execution mode is formed by III group-III nitride compound semiconductor, through above-mentioned sputtering method on basalis 14a laminated ground film forming.
As n type contact layer 14b, with basalis 14a likewise preferably by Al xGa 1-xN layer (0≤x≤1, preferred 0≤x≤0.5, further preferred 0≤x≤0.1) constitutes.In addition, preferably be doped with n type impurity, when with 1 * 10 17～1 * 10 19/ cm 3Concentration, preferably with 1 * 10 18～1 * 10 19/ cm 3Concentration when containing n type impurity, be preferred from keeping with the good Ohmic contact of negative pole, suppressing that crackle takes place, keeps good crystalline viewpoint.As n type impurity, not special the qualification can be enumerated for example Si, Ge and Sn etc., is preferably Si and Ge.Growth temperature and basalis 14a are same.In addition, as above-mentioned, n type contact layer 14b can be the formation of double as basalis.
Constitute the gallium nitride compound semiconductor of basalis 14a and n type contact layer 14b, be preferably same composition, their total thickness is set at 0.1～20 μ m, be preferably set to 0.5～15 μ m, further be preferably set to the scope of 1～12 μ m.When thickness during, can keep semi-conductive crystallinity well in this scope.
(n type coating)
Said n type contact layer 14b and after between the luminescent layer 15 stated, n type coating 14c preferably is set.Through n type coating 14c is set, but landfill results from the deterioration of flatness on the surface of n type contact layer 14b.N type coating 14c can use known mocvd method etc. in the past, utilizes film forming such as AlGaN, GaN, GaInN.In addition, also can be the heterojunction of these structures or repeatedly range upon range of superlattice structure.When being GaInN, certainly preferably the band gap than the GaInN of luminescent layer 15 is big.
The thickness of n type coating 14c does not limit especially, but is preferably the scope of 5～500nm, the more preferably scope of 5～100nm.
In addition, the n type concentration of dopant of n type coating 14c is preferably 1 * 10 17～1 * 10 20/ cm 3Scope, more preferably 1 * 10 18～1 * 10 19/ cm 3Scope.Concentration of dopant considers it is preferred from the aspect of keeping good crystallinity and reducing the operating voltage of light-emitting component when this scope.
" p type semiconductor layer "
P type semiconductor layer 16 is made up of p type coating 16a and p type contact layer 16b usually, can use known in the past mocvd method to wait film forming.In addition, also can be that p type contact layer double as is the formation of p type coating.
(p type coating)
As p type coating 16a, so long as for than after state the big composition of band-gap energy of the luminescent layer 15 of details, can not seal to the charge carrier of luminescent layer 15 is just special and limit, can preferably enumerate Al dGa 1-dThe composition of N (0＜d≤0.4, preferred 0.1≤d≤0.3).When p type coating 16a is formed by such AlGaN, in sealing to being preferred aspect the charge carrier of luminescent layer 15.The thickness of p type coating 16a does not limit especially, but is preferably 1～400nm, more preferably 5～100nm.The p type concentration of dopant of p type coating 16a is preferably 1 * 10 18～1 * 10 21/ cm 3, more preferably 1 * 10 19～1 * 10 20/ cm 3P type concentration of dopant can not reduce crystallinity and obtains good p type crystallization when this scope.
(p type contact layer)
As p type contact layer 16b, be to comprise Al at least eGa 1-eThe gallium nitride system compound semiconductor layer of N layer (0≤e＜0.5, preferred 0≤e≤0.2, further preferred 0≤e≤0.1).When Al consisted of above-mentioned scope, good crystallinity reached and the aspect of the good Ohmic contact of p Ohmic electrode (optically transparent electrode of stating after the reference 17) is preferred from keeping.
In addition, when with 1 * 10 18～1 * 10 21/ cm 3The concentration of scope when containing p type alloy, from keep with the good Ohmic contact of negative pole, suppressing crackle, good crystalline viewpoint takes place, keeps is preferred, more preferably 5 * 10 19～5 * 10 20/ cm 3Scope.
As p type impurity, not special the qualification can preferably be enumerated for example Mg.
The thickness of p type contact layer 16b is not special to be limited, and is preferably 10～500nm, more preferably 50～200nm.Thickness is preferred from the viewpoint of luminous power output when this scope.
< luminescent layer >
Luminescent layer 15 is to be laminated on the p type semiconductor layer 14, and the range upon range of top layer with it of p type semiconductor layer 16, can use in the past known mocvd method etc. to carry out film forming.In addition; Luminescent layer 15; That kind as shown in Figure 1; Be that the trap layer 15b that form with the barrier layer 15a that will be formed by gallium nitride compound semiconductor with by the gallium nitride compound semiconductor that contains indium is alternately range upon range of repeatedly, and in the sequential cascade ground formation of n type semiconductor layer 14 sides and p type semiconductor layer 16 sides configuration barrier layer 15a.
In addition, in the example that Fig. 1 representes, luminescent layer 15 is following formation: the trap layer 15b of 6 layers barrier layer 15a and 5 layers is alternately range upon range of repeatedly, at the superiors and the orlop configuration barrier layer 15a of luminescent layer 15, configuration trap layer 15b between each barrier layer 15a.
As barrier layer 15a, for example can preferably use band-gap energy than the big Al of trap layer 15b that forms by the gallium nitride compound semiconductor that contains indium cGa 1-cThe gallium nitride compound semiconductor of N (0≤c＜0.3) etc.
In addition, in trap layer 15b,, for example can use Ga as the gallium nitride compound semiconductor that contains indium 1-sIn sThe indium gallium nitride of N (0＜s＜0.4) etc.
In addition, as the overall thickness of luminescent layer 15, not special the qualification preferably can obtain quantum and imitate the thickness of hard degree, be critical film thickness.For example, the thickness of luminescent layer 15 is preferably the scope of 1～500nm, more preferably the thickness about 100nm.Thickness helps to improve luminous power output when above-mentioned scope.
< light transmission is anodal >
Light transmission positive pole 17 is electrodes of the light transmission of formation on the p type semiconductor layer 16 of the laminated semiconductor of as above-mentioned, making 10.
As the material of the transparency anodal 17, not special the qualification, the customary means of available this known is provided with ITO (In 2O 3-SnO 2), AZO (ZnO-Al 2O 3), IZO (In 2O 3-ZnO), GZO (ZnO-Ga 2O 3) material that waits.
In addition, its structure also can have no restrictedly to use and comprises any structure of known structure in the past.
Light transmission positive pole 17 can form with roughly whole mode on the p semiconductor layer 16 that covers doped with Mg, can also vacate the gap and form with trellis, tree shape.After forming light transmission anodal 17, implement sometimes with alloying or the transparent thermal annealing that turns to purpose, but also can not implement.
< positive terminal pad and negative pole >
Positive terminal pad 18 is the electrodes that on above-mentioned light transmission anodal 17, form.
As the material of positive terminal pad 18, the various structures of having used Au, Al, Ni and Cu etc. are arranged as everyone knows, can have no the positive terminal pad of restrictedly using these material known, structure.
The thickness of positive terminal pad 18 is preferably in the scope of 100～1000nm.In addition, on the characteristic of pad, when its thickness was big, zygosity increased, so the thickness of positive terminal pad 18 is more preferably more than the 300nm.And then the viewpoint from manufacturing cost is preferably below the 500nm.
Negative pole 19 stacks gradually on substrate 11 in the semiconductor layer of n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, forms with the mode that contacts with the n type contact layer 14b of n type semiconductor layer 14.
For this reason, when forming negative terminal pad 17, remove the part of luminescent layer 15, p type semiconductor layer 16 and n type semiconductor layer 14, form the regional 14d that exposes of n type contact layer 14b, form negative pole 19 above that.
As the material of negative pole 19, the negative pole of various The Nomenclature Composition and Structure of Complexes is well-known.Can have no and restrictedly use these known negative poles, the customary means that can be utilized in this known is provided with.
Manufacturing approach according to the III group-III nitride compound semiconductor light-emitting device of this execution mode of that kind as described above through above-mentioned formation, can adopt sputtering method to form the crystalline film that has good uniformity at short notice.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.
The manufacturing approach of this execution mode; Through under these conditions; At least use sputtering method form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the layer of semiconductor layer 20, can generate high bias voltage or high-power reactive material thus, and can supply with these reactive materials to substrate 11 with high kinergety; Therefore on substrate 11, move, easily with the dislocation cyclisation.Thus, the basalis 14a of n type semiconductor layer 14, can former state ground inherit on substrate 11 film forming as the crystallinity of the resilient coating 12 of the aggregate of column crystallization.Thus, can form the good semiconductor layer that forms by III group-III nitride compound of crystallinity.
In addition, in this execution mode, use sputtering method to form semiconductor layer at least, therefore can improve film forming speed, can shorten film forming (manufacturing) time.And then, through shortening manufacturing time, can the indoor situation that impurity gets in the sputter equipment be suppressed to be Min..
Thereby, the III group-III nitride compound semiconductor light-emitting device that can obtain the productivity ratio excellence and have the excellent characteristics of luminescence.
[lamp]
That kind as described above can utilize the means that well known to a person skilled in the art to constitute lamp through combination III group-III nitride compound semiconductor light-emitting device of the present invention and fluorophor.All the time, known have a technology that changes illuminant colour through illuminated in combination element and fluorophor, can have no and restrictedly adopt such technology.
For example, through suitable selected fluorophor, can obtain the luminous of the wavelength longer than light-emitting component, in addition, the emission wavelength through mixed luminescence element self and by the wavelength of fluorophor conversion can be made into and presents white luminous lamp.
In addition, as lamp, can be used for any purposes of lateral emitting (side view) type of general purpose bullet cut, portable purposes backlight, top light emitting (top view) type that in display, uses etc.
For example; As the example that Fig. 4 representes; In the time of will being mounted to bullet cut with the III group-III nitride compound semiconductor light-emitting device 1 of an electrode type, (being frame 31 among Fig. 4) in two frames gone up bonding light-emitting component 1, in addition; Engage with frame 32 with the negative pole (with reference to the symbol of representing among Fig. 3 19) of line 34, engage with frame 31 with the positive terminal pad (with reference to the symbol of representing among Fig. 3 18) of line 33 with light-emitting component 1 with light-emitting component 1.Then, the periphery of light-emitting component 1 is carried out moulding, can be made into the lamp 3 of bullet cut shown in Figure 4 through the mold 35 that forms by transparent resin.
In addition, III group-III nitride compound semiconductor light-emitting device of the present invention except above-mentioned light-emitting component, also can be used for the photo-electric conversion element of laser diode, photo detector etc. or the electronic device of HBT, HEMT etc. etc.The known semiconductor element that multiple various structures are arranged of these semiconductor elements, the component structure of the laminated structure of III group-III nitride compound semiconductor light-emitting device of the present invention comprises these known elements structures and has no restriction.
Embodiment
Then, more specify the manufacturing approach of III group-III nitride compound semiconductor light-emitting device of the present invention, but the present invention is not only for due to these embodiment through embodiment.
[embodiment 1]
Fig. 1 representes the cross section ideograph of the laminated semiconductor of the III group-III nitride compound semiconductor light-emitting device that this experimental example is made.
In this example, on the c of the substrate that constitutes by sapphire 11 face, use the RF sputtering method to form the aggregate of the column crystallization that forms by AlN,, use the RF sputtering method to form the layer that forms by GaN above that as basalis 14a as resilient coating 12.
At first, by only one side being carried out the substrate 11 that mirror ultrafinish to the sapphire that can be used for epitaxially grown degree constitutes, do not carry out the pre-treatment of wet type particularly etc. and import in the sputter equipment.Here,, used to have the high frequency type power supply as sputter equipment, and have can be in target the device of the mechanism of the position of moving magnet.
Then, in sputter equipment, substrate 11 is heated to 750 ℃, only import nitrogen with the flow of 15sccm after, indoor pressure is remained on 0.08Pa, apply the high frequency bias of 50W in substrate 11 sides, be exposed in the nitrogen plasma, wash substrate 11 surfaces thus.
Then, after in sputter equipment, importing argon and nitrogen, make the temperature of substrate 11 be reduced to 500 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias the time, apply 1W/cm in metal A l target side 2Power, keeping the pressure in the stove is 0.5Pa, under with 5sccm circulation argon gas, condition with 15sccm circulation nitrogen (ratio of nitrogen in gas is all is 75%), on the substrate that is made up of sapphire 11, forms the resilient coating 12 that is made up of AlN.The speed of growth is 0.12nm/ second.
Magnet in the time of washing arbitrary during substrate 11 and during film forming in the rotary target.
Then, carry out the processing of stipulated time, behind the AlN film (resilient coating 12) of formation 50nm, stop plasma work, reduce the temperature of substrate 11 according to the film forming speed of measuring in advance.
Then, from sputter equipment, take out the substrate 11 that has formed resilient coating 12, be transported in the other sputter equipment, use sputtering method to form the sample of GaN layer (III group-III nitride semiconductor) according to following sequentially built.Here,, use to have high-frequency power supply, and have through magnet and scan in the dimetric Ga target device of the mechanism of the position that removable magnetic field applies as the sputter equipment that forms the GaN layer.In addition, the pipe arrangement of circulation refrigerant is set in the Ga target, the refrigerant that is cooled to 20 ℃ is circulated in pipe arrangement, the fusing of the Ga that prevents to cause by heat.
At first, behind indoor importing argon gas and nitrogen, the temperature of substrate 11 is warming up to 1000 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias, simultaneously apply 1W/cm in metal Ga target side 2Power, when keeping indoor pressure to be 0.5Pa, under with 5sccm circulation argon gas, condition (ratio of nitrogen in gas is all is 75%) with 15sccm circulation nitrogen, on the substrate that constitutes by sapphire 11, forms by GaN constitute layer.The speed of growth of this moment is approximately 0.12nm/ second.Then, form the GaN layer of 6 μ m after, stop to produce plasma.
Then, under same condition, formation has 1 * 10 19Cm -3The GaN layer of doping Si of 2 μ m of electron concentration.Each condition of film forming and unadulterated GaN layer are same, towards being arranged at indoor Si target, shining the ion of being emitted by ion gun and take out Si, doping Si.
Through above operation, on the substrate that constitutes by sapphire 11, form have column structure, by the resilient coating 12 that AlN constitutes, form the GaN layer (basalis 14a) of the thickness of 6 μ m above that with unadulterated form, form above that again and have 1 * 10 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration, made the sample of embodiment 1.This specimen surface appears water white specular.
Then, use X ray analyzer (パ Na リ テ イ カ Le society system; Four crystallization X ray determinators, model: X ' pert) measure the X ray swing curve (XRC) of the unadulterated GaN layer (basalis 14a) that obtains through said method.This measure to use Cu β ray X ray the source to take place as light source, is carrying out as (0002) face of the plane of symmetry with as (11-20) face of asymmetric.Usually, under the situation of III group-III nitride compound semiconductor, the wide index that becomes the flatness (モ ザ イ シ テ イ) of crystallization of the XRC spectrum half value of (0002) face, (11-20) wide dislocation density (helical form that becomes of the XRC spectrum half value of face; Twist) index.The result of this mensuration, the unadulterated GaN layer that utilizes manufacturing approach of the present invention to make shows the wide 180arcsec of half value in the mensuration of (0002) face, for (11-20) face, show the wide 300arcsec of half value.
[embodiment 2]
In this example, with the same condition of embodiment 1 under in the unadulterated GaN crystallization (basalis 14a) of 6 μ m of film forming, use identical sputter equipment, form the n type contact layer 14b of the Si that mixed.
Then, sample is imported in the MOCVD stove, form each layer on it, finally made the epitaxial wafer with epitaxial layer structure (laminated semiconductor 10) that the III group-III nitride compound semiconductor light-emitting device represented like Fig. 1 is used.
This epitaxial wafer has following structure: on the substrate that is made up of the sapphire with c face 11; Through the growing method same with embodiment 1; Formation begins sequentially range upon range of from substrate 11 sides after having the resilient coating 12 that is made up of AlN of column structure: the basalis 14a that is formed by unadulterated GaN of 6 μ m, by having 1 * 10 19Cm -3The n type contact layer 14b that constitutes of the GaN of 2 μ m of electron concentration by doping Si, have 1 * 10 18Cm -3The In of 20nm of electron concentration 0.1Ga 0.9N type coating (n type coating 14c), start from the GaN barrier layer and end at the GaN barrier layer laminated construction, it is alternately range upon range of that bed thickness is arranged is the unadulterated In that 6 layers barrier layer 15a constituting of the GaN of 16nm and bed thickness are 3nm 0.2Ga 0.8The luminescent layer (multi-quantum pit structure) 15 that 5 layers the trap layer 15b that N constitutes forms, Al by doped with Mg with 5nm 0.1Ga 0.9 P type coating 16a that N constitutes and the Al of thickness 200nm by doped with Mg 0.02Ga 0.98The p type semiconductor layer 16 of the p type contact layer 16b that N constitutes.
By above order, make the epitaxial wafer that semiconductor light-emitting elements is used with epitaxial layer structure.Here, by the Al of doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes even be not used for the annealing in process with p type carrier activation, also demonstrates p type characteristic.
Then; Using has the epitaxial wafer (with reference to the laminated semiconductor 10 of Fig. 1) of epitaxial layer structure in the substrate that is made up of sapphire 11 laminated as above-mentioned, making is as a kind of light-emitting diode (with reference to the light-emitting component 1 of Fig. 2 and Fig. 3) of semiconductor light-emitting elements.
At first, for the wafer of making, through known photoetching process at Al by doped with Mg 0.02Ga 0.98On the surface of the p type contact layer 16b that N constitutes, form the light transmission anodal 17 that constitutes by ITO and have above that from the anodal face side positive terminal pad 18 of structure of Ti, Al, Au that begun sequential cascade.In addition, the part of wafer is implemented dry ecthing, expose the regional 14d that exposes on the n type contact layer 14b, on this part, make by these 4 layers of negative poles that constitutes 19 of Ni, Al, Ti and Au.Through these operations, on wafer, made each electrode with shape of representing like Fig. 2 and Fig. 3.
For this has formed the wafer of electrode on two-layer in p type semiconductor layer and n type semiconductor layer as above-mentioned; Grind the dorsal part of cutting and grind substrate 11; Process specular face, cut into the square foursquare chip of 350 μ m, each electrode carries up and places on the lead frame; Through being connected in lead frame, processed semiconductor light-emitting elements with gold thread.The forward current that between the electrode of the positive terminal pad 18 of this semiconductor light-emitting elements (light-emitting diode) and negative pole 19, circulates, the forward voltage under the electric current 20mA is 3.0V.In addition, observe luminance through the light transmission anodal 17 of p side, emission wavelength is 470nm, and luminous power output shows 15mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 3]
In this example; On the c of the substrate that constitutes by sapphire face; As resilient coating; Use the RF sputter equipment of rotating cathode formula to form the aggregate of the column crystallization of AlN, above that, identical sputter equipment forms GaN layer (basalis 14a and n type contact layer 14b) when utilizing the resilient coating that is made up of AlN with formation.Then, adopt mocvd method and embodiment 2 likewise to form the light-emitting component semiconductor laminated structure above that.
The temperature of the substrate during the sputter resilient coating is 700 ℃, and the temperature of the substrate when forming basalis is 900 ℃.Other membrance casting condition is all identical with embodiment 2.
Then, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.By the AlN layer (resilient coating) of RF spatter film forming, that can confirm to become crystal grain widely is the column crystallization about 50nm.In addition, whole of resilient coating covered substrate and forming.
Then, the wafer that will as above-mentioned, make is likewise processed light-emitting diode chip for backlight unit with embodiment 2.The forward current that between electrode, circulates, the forward voltage under the electric current 20mA is 3.1V.In addition, luminous through anodal 17 observations of the light transmission of p side, emission wavelength is 460nm, and luminous power output shows 13mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 4]
In this example; On Si (111) substrate, as resilient coating, the RF sputter equipment of use rotating cathode formula forms the aggregate of the column crystallization of AlGaN; Above that; As basalis, use with embodiment 1 identical device and form the AlGaN layer of doping Si, and then form above that and light-emitting component semiconductor laminated structure that embodiment 2 is same.Here, the Al of resilient coating consists of 70%, and the Al of basalis consists of 15%.In addition, the temperature of the substrate during sputter is 500 ℃, and the film-forming temperature of basalis is 700 ℃.Other membrance casting condition is all identical with embodiment 1.
In embodiment 4, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.By the GaAlN layer (resilient coating) of RF spatter film forming, the width that can confirm to become crystal grain is the column crystallization about 30nm.In addition, whole of resilient coating covered substrate and forming.
Then, the wafer that will as above-mentioned, make is likewise processed light-emitting diode chip for backlight unit with embodiment 2.In this example, semiconductor laminated structure side and substrate-side be provided with each electrode up and down, the forward current that between electrode, circulates, the forward voltage under the electric current 20mA are 2.9V.
In addition, luminous through the anodal observation of the light transmission of p side, emission wavelength is 460nm, and luminous power output shows 10mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 5]
In this example; On ZnO (0001) substrate,, use the RF magnetron sputtering method to form the aggregate of the column crystallization of GaN as resilient coating; Above that; As basalis, use the layer that forms the AlGaN of doped with Ge with embodiment 1 identical device, and then employing above that forms the light-emitting component semiconductor laminated structure with embodiment 2 same methods.
Here, the Al of basalis consists of 10%.In addition, the temperature of the substrate when carrying out the sputter of resilient coating is a room temperature, and the temperature of the substrate when carrying out the basalis film forming is 750 ℃.In addition, in this example,, increased the material flow of the In that contains in the luminescent layer in order to attempt making near the green LED the 525nm.
In embodiment 5, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.The GaN layer, the width that can confirm to become crystal grain is the column crystallization about 5nm.In addition, whole of resilient coating covered substrate and forming.
Then, the wafer that will as above-mentioned, make adopts with embodiment 2 same methods and processes light-emitting diode chip for backlight unit, in addition, likewise is provided with each electrode up and down in laminated construction side and substrate-side with embodiment 4.Then, the forward current that between electrode, circulates, the forward voltage under the electric current 20mA are 3.3V.In addition, luminous through the anodal observation of the light transmission of p side, emission wavelength is 525nm, and luminous power output shows 10mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
Can know by above result, III group-III nitride compound semiconductor light-emitting device of the present invention, productivity ratio is excellent, and has the excellent characteristics of luminescence.
(second execution mode)
In this execution mode,, identical with above-mentioned first execution mode for the item beyond the item of following record.
In this execution mode, as the important parameter that uses in the sputtering film-forming, can enumerate bias voltage, put on pressure in the power, substrate temperature, stove of target, nitrogen partial pressure, film forming speed etc.
In the manufacturing approach of this execution mode, when forming semiconductor layer with sputtering method, the bias value that puts on substrate 11 is preferably 0.1W/cm 2More than, 0.2W/cm more preferably 2More than, most preferably be 0.5W/cm 2More than.
Through making the bias value that puts on the substrate 11 is above-mentioned scope, can generate high bias reactive material, in addition, can supply with these reactive materials to substrate 11 with high kinergety, so the migration on the substrate 11 comes to life, and makes the dislocation cyclisation easily.
In addition, in the manufacturing approach in execution mode, when forming semiconductor layer with sputtering method, the power that puts on metallic target (sputtering target) 47 is preferably 0.1W/cm 2～100W/cm 2Scope, 1W/cm more preferably 2～50W/cm 2Scope, most preferably be 1.5W/cm 2～50W/cm 2Scope.
Through making the power that puts on metallic target 47 is above-mentioned scope, and generates the reactive material of big power, in addition, can supply with these reactive materials to substrate 11 with high kinergety, so the migration on the substrate 11 comes to life, and makes the dislocation cyclisation easily.
(the 3rd execution mode)
For the item beyond the item of following record, identical with above-mentioned first execution mode.
The manufacturing approach of this execution mode is when forming above-mentioned semiconductor layer, in the chamber that is used for sputter (with reference to the symbol 41 of Fig. 7), supplies with nitrogen (N 2) and argon (Ar) method of carrying out sputter.
In addition, the manufacturing approach of this execution mode is when forming above-mentioned semiconductor layer, and making above-mentioned indoor pressure is the method below the 10Pa.
In addition, the manufacturing approach of this execution mode is that temperature when forming above-mentioned semiconductor layer, aforesaid substrate is the method for 400 ℃～1300 ℃ scope.
In addition, the manufacturing approach of this execution mode is that film forming speed when forming above-mentioned semiconductor layer is the method for the scope of 0.1～10nm/ second.
In addition, resilient coating 12 can form with the mode that except the surperficial 11a of substrate 11, also covers the side, and then, also can form with the mode at the back side of going back covered substrate 11.
Negative pole 19 stacks gradually on substrate 11 in the semiconductor layer of n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, forms with the mode that contacts with the n type contact layer 14b of n type semiconductor layer 14.
Therefore, when negative pole 19 is set,, form the regional 14d that exposes of n type contact layer 14b, form negative pole 19 above that through removing the part of p type semiconductor layer 16, luminescent layer 15 and n type semiconductor layer 14.
As the material of negative pole 19, the negative pole of various The Nomenclature Composition and Structure of Complexes is known, can have no and restrictedly use these known negative poles, and known customary means is provided with in this technical field capable of using.
[manufacturing approach of light-emitting component]
Below, an example of the manufacturing approach of the light-emitting component of representing for Fig. 2 and Fig. 31 describes.
The manufacturing approach of light-emitting component of the present invention as above-mentioned, is to be included on the substrate 11 to adopt sputtering method to form the method for the operation of the semiconductor layer that is made up of the III group-III nitride compound semiconductor that contains as the Ga of III family element.
In order to use sputtering method on substrate 11, to form the excellent III group-III nitride compound semiconductor layer of crystallinity, must generate more high-octane reactive material, make the migration on the substrate active, in this execution mode the method for following detailed description therefore.
< manufacturing approach of laminated semiconductor >
In the manufacturing approach of this execution mode, on substrate 11, make the crystallization of III group-III nitride compound semiconductor carry out epitaxial growth, when forming laminated semiconductor 10 as shown in Figure 1, on substrate 11, form resilient coating 12, form semiconductor layer 20 above that.In this execution mode, constitute among each layer of semiconductor layer 20, adopt sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14.Then, use mocvd method to form n type coating 14c, luminescent layer 15, the p type coating 16a that constitutes p type semiconductor layer 16 and each layer of p type contact layer 16b of formation n type semiconductor layer 14 above that.
" formation of resilient coating "
When on substrate 11, forming resilient coating 12, preferably substrate 11 is carried out the pre-treatment of wet type.For example, for the substrate that is made up of silicon 11, the RCA washing methods that enforcement is known makes the surface be the hydrogen terminal, makes film-forming process stable.
In addition, before importing back in the reactors at substrate 11, forming resilient coating 12, can use the method for sputtering method etc. to carry out pre-treatment.Specifically, through substrate 11 is exposed to Ar, N 2Plasma in put the surface in order.For example, the action of plasma through making argon gas, nitrogen etc. can be removed the organic substance and the oxide that are attached to substrate 11 surfaces in substrate 11 surfaces.At this moment, if between substrate 11 and chamber, apply voltage, then plasma particle acts on substrate 11 efficiently.
After carrying out the pre-treatment on substrate 11 surface, in sputter equipment, import argon gas and nitrogen, reduce about the temperature to 500 ℃ of substrate 11.Then, when substrate 11 sides apply high frequency bias, apply power, the pressure in the stove is remained certain the time, on substrate 11, form the resilient coating 12 that constitutes by AlN in the Al target side that constitutes by metal A l.
On substrate 11, form the method for resilient coating 12; Not special the qualification; Except sputtering method, for example can enumerate mocvd method, pulsed laser deposition (PLD) method, pulsed electron beam deposition (PED) method etc., can suitably select to use; But, be preferable methods therefore because sputtering method is the easiest and be suitable for volume production.In addition, when using the DC sputter, can cause the charging on target surface, have the unsettled possibility of film forming speed, therefore be preferably pulsed D C sputtering method or RF sputtering method.
The resilient coating 12 of film forming on substrate 11 preferably to contain the composition film forming of Al, especially preferably carries out film forming with the composition that contains AlN.In addition, as the material that is used for resilient coating 12, so long as the III group-III nitride compound semiconductor of being represented by general formula AlGaInN then can use any material.And then, also can form the As that contains as V family, the composition of P carries out film forming.
Making resilient coating 12 is when containing the composition of Al, wherein to be preferably GaAlN, and at this moment, the composition of Al is preferably more than 50%.
In addition,, can become the column crystallization aggregate efficiently through form resilient coating 12 by AlN, thereby more preferably.
In addition, as above-mentioned, resilient coating 12 can form with the mode that except the surperficial 11a of covered substrate 11, also covers the side, and then, also can form with the mode at the back side of going back covered substrate 11.
But when adopting film build method formation resilient coating in the past, the film forming that need carry out at most about 6 times～8 times is handled, and becomes long operation.As the film build method beyond this, also can consider through substrate is not kept being arranged at indoorly, carry out the method for film forming at substrate comprehensively, but when the needs heated substrates, worry that device becomes complicated.
Therefore, for example can consider on one side through substrate being shaken or rotatablely move, with respect to the position of the sputter direction change substrate of filmogen, Yi Bian carry out the method for film forming.According to such method, can adopt once operation with the surface and the side film forming of substrate, then through carrying out film formation process to substrate back, can be to add up to twice operation covered substrate comprehensive.
In addition, filmogen source (target) constitutes for what produced by large-area generation source, and, through the occurrence positions of mobile material, moving substrate and getting final product not in the method that substrate carries out film forming comprehensively.As such method, can enumerate out, as above-mentioned, on one side through magnet being shaken or rotatablely move, the position of the magnet of swap cathode in target is carried out the RF sputtering method of film forming on one side.
In addition, when carrying out film forming, can adopt the method for moving substrate side and cathode side through such RF sputtering method.And then through will as the cathode arrangement in the generation source of material near substrate, the plasma that takes place not being supplied in substrate with pencil, but becoming the formation of supplying with the mode that substrate is wrapped into, film forming becomes possibility in the time of substrate surface and side.
" formation of semiconductor layer "
Through on resilient coating 12, stack gradually n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, and form semiconductor layer 20.In the manufacturing approach of this execution mode; As above-mentioned, among each layer that constitutes semiconductor layer 20, use sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14; In addition, use mocvd method to form n type coating 14c, luminescent layer 15 and p type semiconductor layer 16.
As the growing method of gallium nitride compound semiconductor, can enumerate MOCVD (Metalorganic Chemical Vapor Deposition), HVPE (hydride vapor growth method), MBE (molecular beam epitaxy) etc., from the preferred mocvd method of the viewpoint of film thickness monitoring property, production.In mocvd method, can use hydrogen (H as carrier gas 2) or nitrogen (N 2); As III family raw material, trimethyl gallium (TMG) or triethyl-gallium (TEG) can be used in the Ga source, can use trimethyl aluminium (TMA) or triethyl aluminum (TEA) as the Al source; Trimethyl indium (TMI) or triethylindium (TEI) can be used as the In source, ammonia (NH can be used as the nitrogenous source of V family raw material 3) or hydrazine (N 2H 4) etc.In addition, as alloy, in the n type, can use monosilane (SiH as the Si raw material 4) or disilane (Si 2H 6), can use germane gas (GeH as the Ge raw material 4), tetramethyl germanium ((CH 3) 4Ge), tetraethyl germanium ((C 2H 5) 4Organic germanium compounds such as Ge).In the MBE method, also the germanium of element state capable of using is as doped source.In the p type, for example can use bis-cyclopentadienyl magnesium (Cp as the Mg raw material 2Mg), two ethyl cyclopentadienyl group magnesium (EtCp 2Mg).
(formation of basalis and n type contact layer)
When forming the semiconductor layer 20 of this execution mode, at first, adopt sputtering method to form the basalis 14a of n type semiconductor layer 14 on resilient coating 12 laminated ground.In addition, on basalis 14a, and then adopt sputtering method to form n type contact layer 14b range upon range ofly.
In the manufacturing approach of this execution mode, adopted when forming basalis 14a and n type contact layer 14b, to the indoor supply nitrogen and the argon that are used for sputter, the operation of carrying out sputter.
In the manufacturing approach of this execution mode, the sputter equipment 40 that for example can use Fig. 7 to represent forms basalis 14a and n type contact layer 14b.The sputter equipment 40 of illustrated example, distributed magnet 42 below sputtering target 47, and this magnet 42, shakes along target platform 43 below sputtering target 47 through omitting illustrated drive unit.Supply with nitrogen and argon gas to chamber 41, on the substrate that is installed on heater 44 11, adopt sputtering method to form semiconductor layer.
Below method when using illustrative sputter equipment among Fig. 7, that form basalis 14a and n type contact layer 14b describe.
At first; Import argon gas and nitrogen after indoor 41; The temperature of substrate 11 is warming up to about 100 ℃, when substrate 11 sides apply high frequency bias, applies power in the sputtering target that constitutes by metal Ga 47 sides; On one side indoor pressure is remained 0.5Pa, on one side formation is made up of unadulterated GaN on substrate 11 basalis 14a.
Then, with the same condition of basalis 14a under, form the n type contact layer 14b that the GaN by doping Si constitutes.At this moment, through by the illustrated Si target radiation of the omission of ion gun in being arranged at chamber 41 ion, take out Si and be doped in the GaN from the Si target.Through such operation, on resilient coating 12, form the basalis 14a that constitutes by unadulterated GaN, and then form the n type contact layer 14b that the GaN by doping Si constitutes above that.
As the sputtering method that in the manufacturing approach of this execution mode, uses, preferably, sputtering target is applied power through using RF (high frequency) sputtering method or DC sputtering method.
In addition, during the reactive sputtering method stated after usually using, can control film forming speed easily, therefore more preferably use the RF sputtering method.
In addition, in the DC sputtering method, when using the reactive sputtering method, when when applying the state of electric field continuously with DC, the sputtering target charging is difficult to improve film forming speed, thus preferred pulse give the pulsed DC sputtering method of bias voltage.
In addition; When adopting sputtering method to form semiconductor layer (being basalis 14a and n type contact layer 14b) in this execution mode; Come the method for film forming through the reactive sputtering method that the nitride raw material is circulated in reactor; Crystallinity can be kept well through the control reaction, and its good crystallinity can be stably reproduced, thus preferred.
In addition, when adopting sputtering method to form semiconductor layer, as the sputter equipment 40 that Fig. 7 representes, preferably with respect to sputtering target 47 rotating magnetic fields or shake magnetic field.
When particularly using the RF sputter, as the method that obtains uniform thickness, preferred on one side at target (sputtering target) on one side in the position of shifting magnetic field carry out film forming.The movement technique of concrete magnet can suitably be selected according to the kind of sputter equipment, for example, magnet is shaken or rotatablely moves.
In addition, when using sputtering method to form the mixed crystal layer, there is the metal that will become target in advance to process the method for the mixture of metal material (can form alloy), in addition, also can be two targets that preparation is made up of different materials, the method for carrying out sputter simultaneously.For example, when forming the film of definite composition, use the target of composite material, when forming several kinds of different film film forming, a plurality of targets are arranged at indoor getting final product.
When adopting sputtering method to form basalis 14a and n type contact layer 14b; The method of carrying out film forming in reactor through the reactive sputtering method that the nitride raw material is circulated can be adopted,, crystallinity can be kept well through the control reaction; Can stably reproduce its good crystallinity, therefore more preferably.In addition, when adopting sputtering method to form basalis 14a and n type contact layer 14b, compare, can make device become easy formation with mocvd method, MBE method etc.
In the manufacturing approach of this execution mode, N 2Flow is with respect to nitrogen (N 2) and the ratio of the flow of argon (Ar) be preferably 20%～98% scope.When being the N that is lower than this scope 2During flow-rate ratio, splash-proofing sputtering metal is attached on the substrate with metallic state.In addition, when being when being higher than the flow-rate ratio of above-mentioned scope, because the amount of Ar is very few, so sputtering rate reduces.
The nitrogen flow is with respect to N 2Ratio with the flow of Ar is preferably 25%～90% scope especially.
In the manufacturing approach of this execution mode, as above-mentioned, make the N in the indoor gas of sputter equipment 2Concentration is high, and then, mix Ar with above-mentioned flow-rate ratio as the big gas of weight.When indoor gas only is N 2The time, owing to knock a little less than the power of metallic target 47, therefore limited film forming speed, in this execution mode,, can improve film forming speed, and can make the migration on the substrate 11 active through mixing with the big Ar of above-mentioned flow-rate ratio and weight.
As the nitrogen raw material that in this execution mode, uses, can have no restrictedly and to use known nitrogen compound usually, but ammonia, N 2Gas is simple to operate, and can obtain more at an easy rate, thereby preferred.
The ammonia decomposition efficiency is good, can carry out film forming with the high speed of growth, but because reactivity or toxicity are high, therefore need remove the evil equipment and detector in addition, must make the material of the member that uses in the reaction unit be the high material of chemical stability.
In addition, when using nitrogen as raw material, as device can be easy to use device, but can not obtain high reaction speed.But, adopt through importing to the method in the device behind the decompositions nitrogen such as electric field or heat, can, so consider and take into account the nitrogenous source that is best suited in installation cost though obtain lowlyer but can be used for the film forming speed of industrial degree than ammonia.
In the manufacturing approach of this execution mode, when forming basalis 14a and n type contact layer 14b, the pressure in the chamber 41 is preferably below the 10Pa, in addition, more preferably below the 5Pa, most preferably is below the 1Pa.Pressure in the chamber 41 can form good basalis 14a of crystallinity and n type contact layer 14b with high efficiency in above-mentioned scope the time.When the pressure in the chamber 41 surpassed 10Pa, worry can not obtain good basalis 14a of crystallinity and n type contact layer 14b.
Moreover the pressure in the chamber 41 when adopting sputtering method to form semiconductor layer is preferably more than the 0.3Pa.Pressure in the chamber 41 is during less than 0.3Pa, and the amount of nitrogen becomes too small, worries to be attached on the substrate 11 with the state that does not become nitride by the metal of sputter.
The result that the inventor etc. carry out deep experiment, research finds that the temperature of the substrate 11 when adopting sputtering method to form semiconductor layer is preferably 400 ℃～1300 ℃ scope.This be because, the temperature of the substrate 11 when improve forming basalis 14a and n type contact layer 14b is easy to generate the migration of atom, the cyclisation of dislocation is carried out easily.In addition, the temperature of the substrate 11 when forming basalis 14a and n type contact layer 14b must be the low temperature of temperature of decomposing than crystallization, therefore preferably less than 1300 ℃.
In addition, be to carry out sputter in the said temperature scope through the temperature that makes substrate 11, can obtain good basalis 14a of crystallinity and n type contact layer 14b.
In the manufacturing approach of this execution mode; The temperature of the substrate 11 when adopting sputtering method to form semiconductor layer through making is that above-mentioned scope improves substrate temperature, thus can be with the motion activation of the reactive material that arrives substrate 11 (from the metal of metallic target 47 taking-ups) at crystal surface.
In addition, the manufacturing approach of this execution mode, the film forming speed when adopting sputtering method to form semiconductor layer is preferably 0.1～10nm/ scope of second.
During second, film-forming process becomes for a long time film forming speed less than 0.1nm/, and waste becomes big on the commercial production.In addition, film forming speed surpasses 10nm/ during second, is difficult to obtain good film.
According to the manufacturing approach of this execution mode,, use sputtering method through under these conditions; Nitrogen and argon are supplied in indoor, form the basalis 14a and the n type contact layer 14b that constitute the n type semiconductor layer 14 among the semiconductor layer 20, can generate high bias voltage or high-power reactive material; In addition; Can this reactive material be supplied to the surface of resilient coating 12 with high kinergety, so on resilient coating 12, produce migration, make the dislocation cyclisation easily.Thus, constitute the basalis 14a of the n type semiconductor layer 14 of semiconductor layer 20, can former state ground inherit the crystallinity as the resilient coating 12 of column crystallization aggregate of on substrate 11 film forming.Therefore, can be formed into membrane efficiency height, productivity ratio excellence, and the excellent III group-III nitride compound semiconductor of crystallinity.
In addition, in the manufacturing approach of this execution mode, use sputtering method, nitrogen and argon are supplied to indoor, form basalis 14a and n type contact layer 14b, so compare, can improve film forming speed, can shorten film forming (manufacturing) time with mocvd method.
Through shortening manufacturing time, can suppress impurity and get into indoor in the sputter equipment to Min..
(formation of n type coating)
In this execution mode, on the n type contact layer 14b that adopts sputtering method to form, use mocvd method to form n type coating 14c.
At this moment, can the substrate that stack gradually the resilient coating 12 that obtains just like above-mentioned that kind, basalis 14a, n type contact layer 14b 11 be imported in the MOCVD stoves, on n type contact layer 14b, form by In through known method in the past 0.1Ga 0.9The n type coating 14c that N constitutes.
(formation of luminescent layer)
On n type coating 14c, adopt mocvd method to form luminescent layer 15.
The luminescent layer as shown in Figure 1 15 that in this execution mode, forms has the laminated construction that starts from the GaN barrier layer and end at the GaN barrier layer, alternately range upon range of 6 layers the barrier layer 15a that is formed by GaN and by unadulterated In 0.2Ga 0.85 layers the trap layer 15b that N constitutes and forming.
In addition, in the manufacturing approach of this execution mode, can adopt known in the past mocvd method to form luminescent layer 15 through using and the identical stove of MOCVD stove that in the film forming of n type coating 14c, uses.
(formation of p type coating and p type contact layer)
On luminescent layer 15, that is, on the barrier layer 15a of the superiors that become luminescent layer 15, adopt mocvd method to form the p type semiconductor layer 16 that comprises p type coating 16a and p type contact layer 16b.
In this execution mode, at first, go up the Al that forms by doped with Mg at luminescent layer 15 (the barrier layer 15a of the superiors) 0.1Ga 0.9The p type coating 16a that N constitutes, and then form Al above that by doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes.
In the manufacturing approach of this execution mode, can adopt known in the past mocvd method to form p type semiconductor layer 16 through using and the identical stove of MOCVD stove that in the film forming of n type coating 14c and luminescent layer 15, uses.
< formation that light transmission is anodal >
Through the method as above-mentioned, be that substrate 11 laminated have on the p type contact layer 16b of laminated semiconductor 10 of resilient coating 12 and semiconductor layer, form the light transmission anodal 17 that constitutes by ITO.
As the formation method of light transmission anodal 17, not special the qualification can adopt the customary means of knowing in the art to be provided with.In addition, its structure can have no restrictedly to use and comprises any structure of known structure in the past.
In addition, though the light transmission of this execution mode anodal 17 is used ITO (In 2O 3-SnO 2) form, but be not limited to this, can use for example AZO (ZnO-Al 2O 3), IZO (In 2O 3-ZnO), GZO (ZnO-Ga 2O 3) wait material to form.
In addition, after the formation light transmission anodal 17, implement sometimes with alloying, the transparent thermal annealing that turns to purpose, but also can not implement.
The formation of positive pole and negative pole)
On the light transmission that forms on the laminated semiconductor 10 anodal 17, further form positive terminal pad 18.
This positive terminal pad 18, known method in the past for example capable of using begins to stack gradually Ti, Al, each material of Au and forms from the face side of light transmission anodal 17.
In addition, when forming negative pole 19, at first remove the part of the p type semiconductor layer 16, luminescent layer 15 and the n type semiconductor layer 14 that on substrate 11, form through methods such as dry ecthings, what form n type contact layer 14b thus exposes regional 14d (with reference to Fig. 2 and Fig. 3).
Then, expose on the regional 14d, for example adopt in the past that known method begins to stack gradually each material of Ni, Al, Ti and Au from exposing regional 14d face side, can form the negative pole 19 of 4 layers of structure at this.
Then; For the wafer that as above-mentioned, on laminated semiconductor 10, is provided with light transmission positive pole 17, positive terminal pad 18 and negative pole 19; Grind the back side of cutting and grinding substrate 11; After forming specular face, for example, can be made into light-emitting element chip (light-emitting component 1) through cutting into the square square of 350 μ m.
Manufacturing approach according to the III group-III nitride compound semiconductor light-emitting device of this execution mode as described above adopts above-mentioned formation, can adopt sputtering method to form the crystalline film that has good uniformity with the short time.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.
In the manufacturing approach of this execution mode, under these conditions, form to constitute the semiconductor layer 20 that forms by the III group-III nitride compound that comprises Ga layer among, when the basalis 14a of n type semiconductor layer 14 and n type contact layer 14b; In chamber 41, carry out sputter through supplying with nitrogen and argon; Can generate high bias voltage or high-power reactive material, in addition, can supply with this reactive material to substrate 11 with high kinergety; Therefore on resilient coating 12, move, easily with the dislocation cyclisation.Thus, the basalis 14a of n type semiconductor layer 14, can former state ground inherit the crystallinity as the resilient coating 12 of the aggregate of column crystallization of on substrate 11 film forming.Thus, can form the good semiconductor layer that constitutes by III group-III nitride compound of crystallinity.
In addition, in this execution mode, as above-mentioned, carry out sputter through supply nitrogen and argon in chamber 41, and form basalis 14a and n type contact layer 14b, therefore can improve the film forming speed of semiconductor layer 20, can shorten film forming (manufacturing) time.And then, through shortening manufacturing time, can the indoor situation that impurity gets in the sputter equipment be suppressed to be Min..
Thereby, the III group-III nitride compound semiconductor light-emitting device that can obtain the productivity ratio excellence and have the excellent characteristics of luminescence.
[lamp]
Through making up III group-III nitride compound semiconductor light-emitting device of the present invention and fluorophor as described above, the means that well known to a person skilled in the art capable of using constitute lamp.All the time, known have a technology that changes illuminant colour through illuminated in combination element and fluorophor, can have no and restrictedly adopt such technology.
For example,, can obtain the luminous of the wavelength longer, in addition,, can be made into the alight that is white in color through the emission wavelength of mixed luminescence element self and the wavelength of changing by fluorophor than light-emitting component through suitably selecting fluorophor.
In addition, as lamp, can be used for any purposes of lateral emitting (side view) type of general purpose bullet cut, portable purposes backlight, top light emitting (top view) type that in display, uses etc.
For example; As the example that Fig. 4 representes; In the time of will being mounted to bullet cut with the III group-III nitride compound semiconductor light-emitting device 1 of an electrode type, (being frame 31 in Fig. 4) in two frames gone up bonding light-emitting component 1, in addition; With line 34 negative pole of light-emitting component 1 (symbol of representing with reference to Fig. 3 19) is engaged with frame 32, the positive terminal pad of light-emitting component 1 (symbol of representing with reference to Fig. 3 18) is engaged with frame 31 with line 33.Then, the periphery of light-emitting component 1 is carried out moulding, process the lamp 3 of bullet cut shown in Figure 4 through the mold 35 that constitutes by transparent resin.
In addition, III group-III nitride compound semiconductor light-emitting device of the present invention except above-mentioned light-emitting component, also can be used for the photo-electric conversion element of laser diode and photo detector etc. or the electronic device of HBT, HEMT etc. etc.These semiconductor elements, the known semiconductor element that a lot of various structures are arranged, the component structure of the laminated structure of III group-III nitride compound semiconductor light-emitting device of the present invention comprises these known elements structures and has no restriction.
Then, illustrate in greater detail the manufacturing approach of III group-III nitride compound semiconductor light-emitting device of the present invention through embodiment, but the present invention is not limited in these embodiment.
[embodiment 6]
Fig. 1 representes the cross section ideograph of the laminated semiconductor of the III group-III nitride compound semiconductor light-emitting device that this experimental example is made.
In this example, on the c of the substrate that constitutes by sapphire 11 face, as resilient coating 12; Use the RF sputtering method to form the aggregate of the column crystallization that constitutes by AlN; As basalis 14a and n type contact layer 14b, use the RF sputtering method to form the layer that constitutes by GaN above that.
At first, by only one side being carried out the substrate 11 that mirror ultrafinish to the sapphire that can be used for epitaxially grown degree constitutes, do not carry out the pre-treatment of wet type particularly etc. and import in the sputter equipment.Here,, used to have the high frequency type power supply as sputter equipment, and have can be in target the device of the mechanism of the position of moving magnet.
Then, in sputter equipment, substrate 11 is heated to 750 ℃, only import nitrogen with the flow of 15sccm after, indoor pressure is remained on 0.08Pa, apply the high frequency bias of 50W in substrate 11 sides, be exposed in the nitrogen plasma, wash substrate 11 surfaces thus.
Then, after in sputter equipment, importing argon and nitrogen, make the temperature of substrate 11 be reduced to 500 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias the time, apply 1W/cm in metal A l target side 2Power, keeping the pressure in the stove is 0.5Pa, under with 5sccm circulation argon gas, condition with 15sccm circulation nitrogen (ratio of nitrogen in gas is all is 75%), on the substrate that is made up of sapphire 11, forms the resilient coating 12 that is made up of AlN.
Magnet in the time of washing arbitrary during substrate 11 and during film forming in the rotary target.
Then, carry out the processing of stipulated time, behind the AlN film (resilient coating 12) of formation 50nm, stop plasma work, reduce the temperature of substrate 11 according to the film forming speed of measuring in advance (0.12nm/ second).
Then, from sputter equipment, take out the substrate 11 that has formed resilient coating 12, be transported in the other sputter equipment, use sputtering method to form the sample of GaN layer (III group-III nitride semiconductor) according to following sequentially built.Here,, use to have high-frequency power supply, and have through magnet and scan in the dimetric Ga target device of the mechanism of the position that removable magnetic field applies as the sputter equipment that forms the GaN layer.In addition, the pipe arrangement of the refrigerant that in the Ga target, is provided for circulating circulates the refrigerant that is cooled to 20 ℃ in pipe arrangement, the fusing of the Ga that prevents to be caused by heat.
At first, behind indoor importing argon gas and nitrogen, the temperature of substrate 11 is warming up to 1000 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias, simultaneously apply 1W/cm in metal Ga target side 2Power, when keeping indoor pressure to be 0.5Pa, under with 5sccm circulation argon gas, with the condition of 15sccm circulation nitrogen (nitrogen is 75% with all ratios of gas), on substrate 11, form the layer (basalis 14a) that constitutes by GaN.The speed of growth of this moment is approximately 1nm/ second.Then, form the GaN layer of 6 μ m after, stop to produce plasma.
Then, under same condition, formation has 1 * 10 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration.Each condition of film forming and unadulterated GaN layer are same, to being arranged at the ion that indoor Si target radiation emitted by ion gun and taking out Si, thus doping Si.
Through above operation, on the substrate that constitutes by sapphire 11, form the resilient coating 12 that has column structure and constitute by AlN, form the GaN layer (basalis 14a) of the thickness of 6 μ m above that with unadulterated form, formation has 1 * 10 above that again 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration, made the sample of embodiment 6.This specimen surface appears water white specular.
Then, use X ray analyzer (パ Na リ テ イ カ Le society system; Four crystallization X ray determinators, model: X ' pert) measure the X ray swing curve (XRC) of the unadulterated GaN layer (basalis 14a) that obtains through said method.This measure to use Cu β ray X ray the source to take place as light source, is carrying out as (0002) face of the plane of symmetry with as (10-10) face of asymmetric.Usually, under the situation of III group-III nitride compound semiconductor, the wide index that becomes the flatness (モ ザ イ シ テ イ) of crystallization of the XRC spectrum half value of (0002) face, (10-10) wide dislocation density (helical form that becomes of the XRC spectrum half value of face; Twist) index.The result of this mensuration, the unadulterated GaN layer that utilizes manufacturing approach of the present invention to make shows the wide 80arcsec of half value in the mensuration of (0002) face, for (11-20) face, show the wide 250arcsec of half value.
[embodiment 7]
In this example, with the same condition of embodiment 6 under in the unadulterated GaN crystallization (basalis 14a) of 6 μ m of film forming, use identical sputter equipment, formed the n type contact layer 14b of doping Si.
Then, sample is imported in the MOCVD stove, form each layer on it, finally made the epitaxial wafer with epitaxial layer structure (laminated semiconductor 10) that III group-III nitride compound semiconductor light-emitting device as shown in Figure 1 is used.
This epitaxial wafer has following structure: on the substrate that is made up of the sapphire with c face 11; Through the growing method same with embodiment 1; Formation begins sequentially range upon range of from substrate 11 sides after having the resilient coating 12 that is made up of AlN of column structure: the basalis 14a that is formed by unadulterated GaN of 6 μ m, by having 1 * 10 19Cm -3The n type contact layer 14b that constitutes of the GaN of 2 μ m of electron concentration by doping Si, have 1 * 10 18Cm -3The In of 20nm of electron concentration 0.1Ga 0.9N type coating (n type coating 14c), start from the GaN barrier layer and end at the GaN barrier layer laminated construction, it is alternately range upon range of that bed thickness is arranged is the unadulterated In that 6 layers barrier layer 15a constituting of the GaN of 16nm and bed thickness are 3nm 0.2Ga 0.8The luminescent layer (multi-quantum pit structure) 15 that 5 layers the trap layer 15b that N constitutes forms, Al by doped with Mg with 5nm 0.1Ga 0.9 P type coating 16a that N constitutes and the Al of thickness 200nm by doped with Mg 0.02Ga 0.98The p type semiconductor layer 16 of the p type contact layer 16b that N constitutes.
By above order, made the epitaxial wafer that semiconductor light-emitting elements is used with epitaxial layer structure.Here, by the Al of doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes even be not used for the annealing in process with p type carrier activation, also demonstrates p type characteristic.
Then; Using has the epitaxial wafer (with reference to the laminated semiconductor 10 of Fig. 1) of epitaxial layer structure in the substrate that is made up of sapphire 11 laminated as above-mentioned, making is as a kind of light-emitting diode (with reference to the light-emitting component 1 of Fig. 2 and Fig. 3) of semiconductor light-emitting elements.
At first, for the wafer of making, through known photoetching process at Al by doped with Mg 0.02Ga 0.98On the surface of the p type contact layer 16b that N constitutes, form the light transmission anodal 17 that constitutes by ITO and have above that from the anodal face side positive terminal pad 18 of structure of Ti, Al, Au that begun sequential cascade.In addition, the part of wafer is implemented dry ecthing, expose the regional 14d that exposes on the n type contact layer 14b, on this part, make by these 4 layers of negative poles that constitutes 19 of Ni, Al, Ti and Au.Through these operations, on wafer, made each electrode with shape of representing like Fig. 2 and Fig. 3.
For this has formed the wafer of electrode on two-layer in p type semiconductor layer and n type semiconductor layer as above-mentioned; Grind the dorsal part of cutting and grind substrate 11; Process specular face, cut into the square foursquare chip of 350 μ m, each electrode carries up and places on the lead frame; Through being connected in lead frame, processed semiconductor light-emitting elements with gold thread.The forward current that between the electrode of the positive terminal pad 18 of this semiconductor light-emitting elements (light-emitting diode) and negative pole 19, circulates, the forward voltage under the electric current 20mA is 3.0V.In addition, observe luminance through the light transmission anodal 17 of p side, emission wavelength is 470nm, and luminous power output shows 15mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
In addition, in embodiment 7, the required time of whole operations that above-mentioned film forming is handled is 8 hours.
[comparative example 1]
In this example, on the c of the substrate that constitutes by sapphire face, as resilient coating; Use the RF sputter equipment of rotating cathode formula, and to make substrate temperature be 700 ℃, form the aggregate of the column crystallization of AlN; In addition, be nitrogen only to indoor gas supplied, and make substrate temperature be 900 ℃ to form basalis; In addition, with the same condition of embodiment 6 and embodiment 7 under, form basalis 14a and n type contact layer 14b through sputter.Then, from reaction unit, take out wafer, but the surface of Visual Confirmation wafer is a minute surface.
Then, on said n type contact layer 14b, adopt mocvd method and embodiment 7 likewise to form the light-emitting component semiconductor laminated structure.
Then, the wafer that will as above-mentioned, make is likewise processed light-emitting diode chip for backlight unit with embodiment 2.The forward current that between electrode, circulates, the forward voltage under the electric current 20mA is 3.5V.In addition, luminous through the anodal observation of the light transmission of p side, emission wavelength is 470nm, and luminous power output shows 9mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of roughly making of the wafer of making comprehensively, does not obtain with can having deviation.
But, in comparative example 1, can confirm that film forming speed is about 1/3 the speed of embodiment 6.In addition, in comparative example 1, the needed time of whole operations that film forming is handled is 14 hours, and it is elongated that result and embodiment 7 compare activity time.
[comparative example 2]
In this example,, likewise operate, on resilient coating 12, adopt sputtering method to form basalis 14a and n type contact layer 14b with embodiment 6 and embodiment 7 except the room pressure that makes sputter equipment is the 15Pa.Then, from reaction unit, take out wafer, the surface haze of wafer can not film forming form light emitting element structure.
[comparative example 3]
In this example,, likewise operate, on resilient coating 12, adopt sputtering method to form basalis 14a and n type contact layer 14b with embodiment 6 and embodiment 7 except the temperature that makes substrate 11 is 200 ℃.Then, from reaction unit, take out wafer, the surface haze of wafer can not film forming form light emitting element structure.
[comparative example 4]
In this example, be 20nm/ second except making film forming speed, likewise operate with embodiment 6 and embodiment 7, on resilient coating 12, adopt sputtering method formation basalis 14a and n type contact layer 14b.Then, from reaction unit, take out wafer, the surface haze of wafer can not film forming form light emitting element structure.
[embodiment 8]
In this example, on ZnO (0001) substrate, as resilient coating; Use the RF magnetron sputtering method to form the aggregate of the column crystallization of GaN;, use the device identical above that, the basalis that formation is made up of the AlGaN of doped with Ge with embodiment 6; On basalis, form the n type contact layer that the AlGaN by doping Si constitutes.Then, and then adopt the method same above that, form the light-emitting component semiconductor laminated structure by mocvd method with embodiment 7.Here, the Al of basalis consists of 10%.In addition, the temperature of the substrate when carrying out the sputter of resilient coating is a room temperature, and the temperature of the substrate when carrying out the film forming of basalis is 750 ℃.In addition, in this example,, increase the material flow of the In that contains in the luminescent layer in order to attempt making near the green LED the 525nm.
In embodiment 8, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
The wafer that to as above-mentioned, make adopts with embodiment 7 same methods and processes light-emitting diode chip for backlight unit, and then, the forward current that between electrode, circulates, the forward voltage under the electric current 20mA are 3.0V.In addition, luminous through the anodal observation of the light transmission of p side, emission wavelength is 525nm, and luminous power output shows 8mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of roughly making of the wafer of making comprehensively, does not obtain with can having deviation.
Can know by above result, III group-III nitride compound semiconductor light-emitting device of the present invention, productivity ratio is excellent, and has the excellent characteristics of luminescence.
Utilize possibility on the industry
By the III group-III nitride compound semiconductor light-emitting device that the present invention obtains, has the superficial layer that constitutes by III group-III nitride compound semiconductor crystallization with well-crystallized property.
Therefore, can make the semiconductor element of light-emitting diode, laser diode or electronic device etc. with excellent characteristics of luminescence.
Among the present invention the expression number range " more than " and " following " include given figure.

Claims (24)

1. the manufacturing approach of an III group-III nitride compound semiconductor light-emitting device; It is the manufacturing approach that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element; It is characterized in that; In with said substrate and the configuration of sputtering target subtend ground; Make the scope that is spaced apart 20～100mm of said substrate and said sputtering target, when forming said semiconductor layer, making the indoor vacuum degree of in sputter, using in advance is 1.0 * 10 -3After below the Pa, to said indoor base feed, the power that puts on sputtering target applies through high-frequency mode or pulsed D C mode.
2. according to the manufacturing approach of the said III group-III nitride of claim 1 compound semiconductor light-emitting device, it is characterized in that, when forming said semiconductor layer, make the magnetic field rotation or magnetic field is shaken with respect to sputtering target.
3. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 and 2 is characterized in that, forms said semiconductor layer through the reactive sputtering method that the nitride raw material is circulated in reactor.
4. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 3 is characterized in that, uses nitrogen as said nitride raw material.
5. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 and 2 is characterized in that, between said substrate and said semiconductor layer, forms the resilient coating that comprises column crystallization.
6. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, adopts sputtering method to form said resilient coating.
7. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, forms said resilient coating by the III group-III nitride compound that contains as the Al of III family element.
8. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 7 is characterized in that, forms said resilient coating by AlN.
9. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, forms said resilient coating with the mode more than at least 90% on the surface that covers said substrate.
10. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, the width that constitutes the column crystallization of said resilient coating is the scope of 0.1～100nm.
11. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, the thickness of said resilient coating is the scope of 10～500nm.
12. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, when forming said resilient coating by AlN, is formed the said semiconductor layer that is formed by III group-III nitride compound by GaN.
13. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5 is characterized in that, said substrate uses sapphire.
14. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, when adopting sputtering method to form said semiconductor layer, making the power density that puts on said substrate is 0.1W/cm 2More than.
15. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, when adopting sputtering method to form said semiconductor layer, making the power density that puts on sputtering target is 0.1W/cm 2～100W/cm 2Scope.
16. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, when forming said semiconductor layer, thereby carries out sputter to the indoor supply nitrogen and the argon that in sputter, use.
17. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, when forming said semiconductor layer, makes the indoor pressure that in sputter, uses as below the 10Pa.
18. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, the temperature of the said substrate when forming said semiconductor layer is 400 ℃～1300 ℃ a scope.
19. the manufacturing approach according to the said III group-III nitride of claim 1 compound semiconductor light-emitting device is characterized in that, the film forming speed when forming said semiconductor layer is 0.1～10nm/ scope of second.
20. manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of claim 16～19; It is characterized in that; On said substrate,, stack gradually each layer and the film forming of n type semiconductor layer, luminescent layer, p type semiconductor layer at least as said semiconductor layer.
21. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 5; It is characterized in that; On said substrate; As said semiconductor layer, stack gradually each layer and the film forming of n type semiconductor layer, luminescent layer, p type semiconductor layer at least, said resilient coating laminated be formed on the basalis that has in the said n type semiconductor layer.
22. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 21 is characterized in that, the thickness of said basalis is more than the 0.1 μ m.
23. an III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacturing approach of claim 1～22 to obtain.
24. a lamp, it has used the described III group-III nitride of claim 23 compound semiconductor light-emitting device.
CN200780030345XA 2006-08-18 2007-08-15 Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp Active CN101506946B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2006223260A JP2008047762A (en) 2006-08-18 2006-08-18 Group iii nitride compound semiconductor light emitting element, process for fabricating the same, and lamp
JP223261/2006 2006-08-18
JP223260/2006 2006-08-18
JP2006223261A JP2008047763A (en) 2006-08-18 2006-08-18 Group iii nitride compound semiconductor light emitting element, process for fabricating the same, and lamp
JP291082/2006 2006-10-26
JP2006291082A JP2008106316A (en) 2006-10-26 2006-10-26 Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp
PCT/JP2007/065902 WO2008020599A1 (en) 2006-08-18 2007-08-15 Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp

Publications (2)

Publication Number Publication Date
CN101506946A CN101506946A (en) 2009-08-12
CN101506946B true CN101506946B (en) 2012-11-21

Family

ID=39181189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200780030345XA Active CN101506946B (en) 2006-08-18 2007-08-15 Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp

Country Status (2)

Country Link
JP (1) JP2008047762A (en)
CN (1) CN101506946B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI415295B (en) * 2008-06-24 2013-11-11 Advanced Optoelectronic Tech Semiconductor component manufacturing method and structure thereof
US8070925B2 (en) * 2008-10-17 2011-12-06 Applied Materials, Inc. Physical vapor deposition reactor with circularly symmetric RF feed and DC feed to the sputter target
JP5855410B2 (en) * 2011-09-29 2016-02-09 株式会社アルバック Method for forming aluminum nitride film
DE102011114671A1 (en) * 2011-09-30 2013-04-04 Osram Opto Semiconductors Gmbh Method for producing an optoelectronic semiconductor chip and optoelectronic semiconductor chip
CN104508795A (en) * 2012-06-15 2015-04-08 欧瑞康高级技术股份公司 Method for depositing group III nitride semiconductor film
WO2014002465A1 (en) * 2012-06-26 2014-01-03 キヤノンアネルバ株式会社 Epitaxial film-forming method, sputtering device, method for manufacturing semiconductor light-emitting element, semiconductor light-emitting element, and illumination device
WO2014008162A1 (en) * 2012-07-02 2014-01-09 Applied Materials, Inc. Aluminum-nitride buffer and active layers by physical vapor deposition
CN103779449A (en) * 2012-10-17 2014-05-07 江苏汉莱科技有限公司 Composite substrate for growing gallium nitride thin film and preparation method and application thereof
JP6458344B2 (en) * 2014-02-27 2019-01-30 東ソー株式会社 Method of manufacturing gallium nitride film and laminated substrate
WO2017094028A1 (en) * 2015-12-02 2017-06-08 Indian Institute Of Technology Bombay Method and apparatus for forming silicon doped gallium nitride (gan) films by a co-sputtering technique
CN109841708B (en) * 2017-11-28 2022-05-31 中国科学院半导体研究所 Semiconductor device and method for manufacturing the same
TWI825187B (en) * 2018-10-09 2023-12-11 日商東京威力科創股份有限公司 Method for forming nitride semiconductor film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001254167A (en) * 2000-03-10 2001-09-18 Ricoh Co Ltd Method of cleaning surface of contamination plate of sputtering system, and contamination plate
CN1425189A (en) * 2000-04-21 2003-06-18 丰田合成株式会社 Method of manufacturing group-III nitride compound semiconductor

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6043482A (en) * 1983-08-20 1985-03-08 Fujitsu Ltd sputtering equipment
JPH1161404A (en) * 1997-08-21 1999-03-05 Hitachi Ltd Electrostatic suction device, manufacturing method thereof, and processing device using the same
JP3749383B2 (en) * 1998-08-25 2006-02-22 株式会社昭和真空 Method and apparatus for controlling film thickness distribution in sputtering apparatus
JP4613373B2 (en) * 1999-07-19 2011-01-19 ソニー株式会社 Method for forming group III nitride compound semiconductor thin film and method for manufacturing semiconductor element
JP3809464B2 (en) * 1999-12-14 2006-08-16 独立行政法人理化学研究所 Method for forming semiconductor layer
JP2005277374A (en) * 2004-02-26 2005-10-06 Toyoda Gosei Co Ltd Group III nitride compound semiconductor light emitting device and method of manufacturing the same
JP4833616B2 (en) * 2004-09-13 2011-12-07 昭和電工株式会社 Method for producing group III nitride semiconductor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001254167A (en) * 2000-03-10 2001-09-18 Ricoh Co Ltd Method of cleaning surface of contamination plate of sputtering system, and contamination plate
CN1425189A (en) * 2000-04-21 2003-06-18 丰田合成株式会社 Method of manufacturing group-III nitride compound semiconductor

Also Published As

Publication number Publication date
JP2008047762A (en) 2008-02-28
CN101506946A (en) 2009-08-12

Similar Documents

Publication Publication Date Title
CN101506946B (en) Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp
CN102017082B (en) Group III nitride semiconductor device and method for manufacturing the same, group III nitride semiconductor light-emitting device and method for manufacturing the same, and lamp
CN101689592B (en) III nitride semiconductor light emitting element, method for manufacturing the iii nitride semiconductor light emitting element, and lamp
EP2056339B1 (en) Method for manufacturing group iii nitride compound semiconductor light-emitting device
TWI413279B (en) Group III nitride semiconductor light-emitting device, method of manufacturing the same, and lamp
CN101438429B (en) Group III nitride compound semiconductor stacked structure
CN101925979B (en) Method for manufacturing III nitride semiconductor, and method for manufacturing III nitride semiconductor light emitting element
US8012784B2 (en) Method for producing group III nitride semiconductor light emitting device, group III nitride semiconductor light emitting device, and lamp
CN101874306A (en) Group III nitride semiconductor light-emitting device, method for manufacturing the same, and lamp
CN102113140A (en) Method for manufacturing iii nitride semiconductor light emitting element, iii nitride semiconductor light emitting element and lamp
KR20090074092A (en) METHOD FOR MANUFACTURING GROUP LIGHT-MILANED SEMICONDUCTOR LIGHT-EMITTING DEVICE,
JP2008109084A (en) Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp
JP2008153603A (en) Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp
JP2008124060A (en) Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp
US7585690B2 (en) Process for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device and lamp
JP2008047763A (en) Group iii nitride compound semiconductor light emitting element, process for fabricating the same, and lamp
CN101517759B (en) Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp
JP2008226868A (en) Group iii nitride compound semiconductor laminated structure
JP2008106316A (en) Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp
JP2008135463A (en) Manufacturing method of group iii nitride semiconductor, manufacturing method of group iii nitride semiconductor light-emitting element, group iii nitride semiconductor light-emitting element and lamp
JP2008159954A (en) Manufacturing method of group iii nitride semiconductor, manufacturing method of group iii nitride semiconductor light-emitting element, group iii nitride semiconductor light-emitting element and lamp
JP5179055B2 (en) Group III nitride semiconductor manufacturing method, group III nitride semiconductor light emitting device manufacturing method, group III nitride semiconductor light emitting device, and lamp
JP2008198705A (en) Method for manufacturing group iii nitride semiconductor light-emitting device, group iii nitride semiconductor light-emitting device, and lamp
JP2008311420A (en) Manufacturing method of sputter target, sputter target, sputtering device, manufacturing method of group iii nitride compound semiconductor light emitting element, group iii nitride compound semiconductor light emitting element, and lamp
JP2008177523A (en) Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: TOYODA GOSEI CO., LTD.

Free format text: FORMER OWNER: SHOWA DENKO K.K.

Effective date: 20130226

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20130226

Address after: Aichi

Patentee after: Toyoda Gosei Co., Ltd.

Address before: Tokyo, Japan, Japan

Patentee before: Showa Denko K. K.