CN1586015A - Ultraviolet emitting device - Google Patents
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- CN1586015A CN1586015A CN02822534.1A CN02822534A CN1586015A CN 1586015 A CN1586015 A CN 1586015A CN 02822534 A CN02822534 A CN 02822534A CN 1586015 A CN1586015 A CN 1586015A
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- 230000004888 barrier function Effects 0.000 claims abstract description 70
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- 239000000463 material Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/822—Materials of the light-emitting regions
- H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
- H10H20/825—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/811—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions
- H10H20/812—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions within the light-emitting regions, e.g. having quantum confinement structures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
- H01S5/343—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
- H01S5/34333—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer based on Ga(In)N or Ga(In)P, e.g. blue laser
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Abstract
直接在晶体基片(B)或在晶体基片(B)上的缓冲层上形成包含GaN系晶体层和发射区的层压结构(S)。发射区具有多个量子势阱结构。这些势阱层由可以发射紫外光的InGaN制成。势阱层的层数为2至20，并且阻挡层的厚度为7至30nm。因此，通过由InGaN制成的发射层，实现了高输出能量的紫外光辐射。为了形成高质量的GaN薄膜，优选直接在AlN低温生长缓冲层上形成AlGaN底层。推荐一种其中不在晶体基片和势阱层之间(在提供AlGaN底层的模式情况下，在AlGaN底层和势阱层之间)形成AlGaN层的模式。
A laminated structure (S) comprising a GaN-based crystal layer and an emitter region is formed directly on the crystal substrate (B) or on a buffer layer on the crystal substrate (B). The emission area has multiple quantum well structures. These potential well layers are made of InGaN that emits ultraviolet light. The number of layers of the potential well layer is 2 to 20, and the thickness of the barrier layer is 7 to 30 nm. Thus, a high output energy of UV radiation is achieved through the emitting layer made of InGaN. In order to form a high-quality GaN thin film, it is preferable to form an AlGaN bottom layer directly on the AlN low-temperature growth buffer layer. A mode is recommended in which an AlGaN layer is not formed between the crystal substrate and the well layer (in the case of the mode in which the AlGaN underlayer is provided, between the AlGaN underlayer and the well layer).
Description
Technical field
The present invention relates to a kind of semiconductor light-emitting elements.More specifically, the present invention relates to a kind of GaN is ultraviolet emitting device, and it comprises InGaN based material with the composition that can the launch ultraviolet light material as luminescent layer.
Background technology
At GaN based light-emitting device such as GaN series LED (LED), GaN is in laser diode (LD) etc., known use InGaN provides light emission efficiently as the light-emitting component (blueness, the green luminousing element that especially, have the luminescent layer that contains high In composition) of luminescent layer.This has been interpreted as being attributable to the localization of charge carrier, reason is that the fluctuation of In composition has reduced the ratio of the charge carrier that is injected into luminescent layer, and it is caught by non-radiative center, and high efficiency light emission is provided again.
When the ultraviolet light that is no more than 420nm will be that LED and GaN are when launching among the LD at GaN, typically with the material of InGaN (In form be no more than 0.15) as luminescent layer.
Generally speaking, the upper limit of ultraviolet wavelength is shorter than under the short wavelength end (380nm-400nm) of visible light and its and is limited to about 1nm (0.2nm-2nm).But in this manual, ultraviolet light comprises by recited above and has the royal purple light that is no more than 420nm that is no more than the InGaN emission that 0.15 In forms.The ultraviolet light wavelength that can be taken place by GaN is 365nm.Therefore, InGaN contains under the situation that In forms and do not contain the ternary compound that Al forms basically therein, and the lower limit of the ultraviolet light wavelength that can take place is longer than 365nm recited above.Below, comprise InGaN and be meant the InGaN ultraviolet emitting device as the ultraviolet emitting device of luminescent layer material.
But because blueness, the green luminousing element of the luminescent layer of forming with high In are compared, the ultraviolet light in the InGaN ultraviolet emitting device has the short wavelength, therefore needs the In that reduces luminescent layer to form.As a result, because the localization effect that fluctuation caused that In recited above forms reduces, the ratio of being caught by non-radiative recombination center reduces, and it stops high output again.
In the InGaN ultraviolet emitting device, the structure of luminous component is single quantum well (SQW) structure or a plurality of quantum well (MQW) structure (in the SQW structure owing to its thin active coating comprises so-called DH structure), and wherein luminescent layer (potential well layer) is clipped in by having (quantum potential well structure also comprises the barrier layer) between the cover layer that more material of high band gap is made.According to list of references (Hiroo Yonezu, Hikari Tsushin Soshi Kogaku, Kougakutosho Ltd., the 72nd page), provide a kind of difference in band gap between luminescent layer and cover layer to be not less than the criterion of " 0.3eV ".
Consider background recited above, when InGaN was used as the emission layer (potential well layer) of emission ultraviolet light, because the restriction of charge carrier, the AlGaN that will have large band gap was used for the cover layer and the barrier layer of clamping luminescent layer.
Figure 6 shows that an embodiment of the component structure of conventional ultraviolet leds, described ultraviolet leds comprises the In as the material of luminescent layer
0.03Ga
0.97N (emission wavelength 380nm).As shown in this Fig, on crystal substrates B10, form n-type GaN contact layer 101 by resilient coating B20, by crystal growth, lamination contains SQW structure (n-type Al in succession on n-type GaN contact layer 101
0.1Ga
0.9 N cover layer 102, In
0.03Ga
0.97N potential well layer (luminescent layer) 103, p-type Al
0.2Ga
0.8N cover layer 104) luminous component and p-type GaN contact layer 105.And, on the n-type GaN contact layer 101 that part exposes, form n-type electrode P10, and on p-type GaN contact layer 105, form p-type electrode P20.
Luminous component shown in Fig. 6 has the SQW structure.When it had the MQW structure when preparation, the barrier layer that need settle between two potential well layers had the thickness that tunnel effect can be provided, and this thickness is generally about 3-6nm.
But although adopted the luminous component of various structures recited above, the InGaN ultraviolet emitting device can not provide enough output, and reason is that the low In of its luminescent layer forms.
Summary of the invention
One object of the present invention is to solve problem recited above, and during as the luminescent layer material, is providing a kind of by making the component structure optimization show the ultraviolet emitting device of higher output with InGaN and another kind of InGaN based material.
The inventor finds, even when the luminescent layer material is when having the InGaN based material of the composition that can launch ultraviolet light, by the structural limitations with luminous component is the MQW structure, and again with the thickness limits on the number of plies of potential well layer and barrier layer in concrete scope, can improve output, this causes of the present invention finishing.Therefore, ultraviolet emitting device of the present invention has following feature:
(1) a kind of ultraviolet emitting device, its be a kind of have comprise crystal substrates and GaN is the GaN based semiconductor light-emitting device of the laminar structure of crystal layer, described GaN is that crystal layer is formed directly into or is formed on the described substrate by resilient coating, wherein said laminar structure comprises the luminous component that contains p-type layer and n-type layer, wherein said luminous component has a plurality of quantum potential well structures, and described potential well layer is to be made by the InGaN based material that can launch ultraviolet light, the number of plies of described potential well layer is 2-20, and the thickness on described barrier layer is 7nm-30nm.
(2) (1) described ultraviolet emitting device above, laminar structure wherein recited above forms on crystal substrates by the AlN low temperature-grown buffer layer, wherein directly forms Al on described AlN low temperature-grown buffer layer
XGa
1-XN (0＜X≤1) basal layer.
(3) (2) described ultraviolet emitting device above, it is at described Al
XGa
1-XThe layer of not making between N (0＜X≤1) basal layer and the described potential well layer by AlGaN.
(4) (1) described ultraviolet emitting device above, the p-type layer in the wherein described in the above laminar structure and the position of n-type layer relation be p-type layer at upside, and p-type contact layer is by In
YGa
1-YN (0＜Y≤1) makes.
(5) (1) described ultraviolet emitting device above, a plurality of quantum potential well structures wherein recited above have the barrier layer that contacts with p-type layer, and the thickness on the described barrier layer that contacts with p-type layer is 10nm-30nm.
(6) it is that the potential well layer made of crystal and the GaN that mixed by Si are the barrier layer that crystal is made that (1) described ultraviolet emitting device above, a plurality of quantum potential well structures wherein recited above comprise by unadulterated GaN.
(7) (1) described ultraviolet emitting device above, a plurality of quantum potential well structures wherein recited above comprise by In
XGa
1-XPotential well layer that N (0＜X≤1) makes and the barrier layer of making by GaN.
(8) (7) described ultraviolet emitting device above, In wherein recited above
XGa
1-XIt is 0＜X≤0.11 that In among the N forms X.
(9) (1) described ultraviolet emitting device above, the layer that it is not made by AlGaN between described crystal substrates and described potential well layer.
(10) (1) described ultraviolet emitting device above wherein carries out recessed-protruding processing in its surface with described crystal substrates, and vapor phase growth GaN be crystal layer cover described recessed-convex portion is with the cambium layer laminated structure.
The accompanying drawing summary
Figure 1 shows that the schematic diagram of an example of ultraviolet emitting device structure of the present invention.In this figure, each symbolic representation is as follows: B: crystal substrates, and S: containing GaN is the laminar structure of crystal layer, 2:n-type cover layer, 3:MQW structure, 4:p-type cover layer; P1:n-type electrode, P2:p-type electrode.
Figure 2 shows that the schematic diagram of a different instances of structure of ultraviolet emitting device of the present invention.
Figure 3 shows that MQW potential well layer the number of plies and according to the curve chart that concerns between the radiative output of measuring in the embodiment of the invention 1.
Figure 4 shows that MQW the obstruction layer thickness and according to the curve chart that concerns between the radiative output of measuring in the embodiment of the invention 2.
Figure 5 shows that in ultraviolet light element of the present invention, adopt the barrier layer carrier concentration (cm of unit of Si doping blocking layer
-3) and radiative output between the curve chart that concerns.
Figure 6 shows that embodiment, wherein an In of the component structure of conventional ultraviolet leds
0.03Ga
0.97N is the material of luminescent layer.
Implement best mode of the present invention
When using in the present invention, GaN system is meant by In
XGa
YAl
ZN (0≤X≤1,0≤Y≤1,0≤Z≤1, X+Y+Z=1) compound semiconductor shown in.For example, as important compound, can mention AlN, GaN, AlGaN, InGaN, InGaAlN etc.
Described in the above In
XGa
YAl
ZAmong the N, the In composition is contained basically in InGaN system and Ga forms, and can be InGaN or the InGaN that is added with the Al composition.
Ultraviolet emitting device of the present invention can be a ultraviolet leds, ultraviolet light LD etc.Below, the present invention makes an explanation as an example with reference to ultraviolet leds.In component structure, any in p-type layer and the n-type layer can be positioned at downside (crystal substrates side).For the production of the GaN based semiconductor that obtains easily high quality crystal etc., the preferred embodiment that wherein forms n-type layer at downside.Below, explain the component structure that wherein forms n-type layer, but be not limited thereto at downside.
Figure 1 shows that an embodiment of the structure (LED component structure) of ultraviolet emitting device of the present invention.As shown in this figure, by GaN is that low temperature-grown buffer layer B1 grows on crystal substrates B and comprises the laminar structure S that GaN is a crystal layer, and laminar structure S contains the luminous component that comprises p-type layer and n-type layer, and contains electrode, forms ultraviolet emitting device of the present invention thus.
Embodiment for Fig. 1, from that side of bottom, being constructed as follows of each layer: sapphire crystal substrate B, GaN low temperature-grown buffer layer B1, unadulterated GaN layer 1, luminous component [n-type GaN cover layer (=contact layer) 2, MQW structure 3 (GaN barrier layer/InGaN potential well layer/GaN barrier layer/InGaN potential well layer/GaN barrier layer), p-type AlGaN cover layer 4], p-type GaN contact layer 5.Partly expose n-type GaN contact layer, forming n-type electrode P1 on the surface of described exposure and on p-type GaN contact layer, forming p-type electrode P2.
The key character of said elements structure is that luminous component has the MQW structure basically, and the material of described MQW structure potential well layer is the InGaN with the composition that can launch ultraviolet light, and the number of plies of potential well layer is 2-20, and the thickness on barrier layer is 7nm-30nm.
By luminous component being limited to such structure,, can provide the output higher than conventional luminescent layer for luminescent layer even use the ultraviolet emitting device of InGaN based material, particularly InGaN.
Luminous component has p-type cover layer and n-type cover layer, and the MQW structure between them.N-type and p-type cover layer also can be as n-type and p-type contact layers.In addition, as required, the component structure of LD etc. can contain ducting layer, protective layer etc. in tectal the inside.
Figure 3 shows that MQW potential well layer the number of plies and according to the curve chart that concerns between the radiative output of measuring among the following embodiment 1.As from then on being clear that in the curve chart, the number of plies of potential well layer should be 2-20, and outside this scope, radiative output is the same with conventional levels low.The number of plies of preferred especially potential well layer is 8 to 15, wherein obtains the highest emission light output.
The material of potential well layer is InGaN based material, particularly In
XGa
1-XN (0＜X≤1, if Ga is necessary, 0＜X＜1), it can have any composition, as long as can launch the ultraviolet light that is no more than 420nm.In
XGa
1-XWhat the In of N formed X is 0＜X≤0.11 with preferred value more specifically.Do not need the material of potential well layer to form for identical In, and can determine aptly that as required wherein said composition can have gradient etc. for all layers.
Potential well layer can have identical thickness with known MQW structure, for example, is 2nm-10nm.
Do not need the barrier layer to exist as contiguous two tectal outermost layers independently.For example, can adopt following embodiment (1) to (3) etc.
(1) in (n-type cover layer/potential well layer/barrier layer/potential well layer/p-type cover layer), one wherein cover layer also be the embodiment on outmost barrier layer.
(2) in (n-type cover layer/barrier layer/potential well layer/barrier layer/potential well layer/barrier layer/p-type cover layer), wherein outmost barrier layer embodiment outside cover layer that has an independent existence.
(3) in (n-type cover layer/potential well layer/barrier layer/potential well layer/barrier layer/p-type cover layer), wherein outmost barrier layer exists only in the embodiment on the side independently.
Among the present invention, the thickness on all barrier layers in the MQW structure all is 7nm-30nm.
Figure 4 shows that the thickness that stops layer and according to the curve chart that concerns between the radiative output of measuring in the following examples.Be clear that as the curve among the figure from then on, when the thickness on barrier layer is 7nm-30nm, can obtain having the ultraviolet emitting device of high emission light output.When the thickness on barrier layer was thinner than 7nm or is thicker than 30nm, it is the same with conventional embodiment low that luminous output becomes.In the thickness range on described barrier layer, particularly preferably be 8nm-15nm in the above, in this scope, can obtain having the light-emitting component of high output.
Though the thickness on the barrier layer of conventional MQW structure is 3nm-6nm, the thickness on the barrier layer among the present invention is 7nm-30nm.By with the thickness increase on barrier layer level so far, wave function is not overlapping, by the barrier layer, obtains the laminated material rather than the MQW structure of a plurality of SQW structures, and enough height output is provided.When the thickness on barrier layer surpasses 30nm, before the hole arrives potential well layer, to catch from p-layer injected holes by dislocation defects etc., described dislocation defects etc. become the non-radiative center that exists in the GaN barrier layer, and it does not preferably reduce luminous efficiency again.
Preferred embodiment as the MQW structure among the present invention, can mention such embodiment, wherein outmost barrier layer always is present on the p-type cover layer side (promptly, embodiment recited above (2) and (3)), and be 10-30nm at the thickness on the outmost barrier layer of p-type side.Embodiment thus, potential well layer are not easy to be subjected to cause the reduction that damages by the heat of the layer of growth after the p-type cover layer and the infringement of gas.In addition, can reduce the diffusion of the dopant material (Mg etc.) that comes from p-type layer, and can be reduced in the distortion on the potential well layer, it provides effect and the effect that not only improves output but also increase component life.
The material on barrier layer can be any material, as long as it is the GaN based semiconductor material with the band gap on the barrier layer that can become the InGaN potential well layer.In the present invention, recommend GaN as preferable material.
In the MQW of routine structure, consider the carrier confinement in the potential well layer, use barrier layer rather than potential well layer with enough broad-band gaps.Especially, under the situation of ultraviolet emitting device, compare with blue-light emitting element etc., because potential well layer itself has wideer band gap, potential well layer need have the material of also wanting broad-band gap.For example, when potential well layer is InGaN (In consists of 0.03), AlGaN is used as barrier layer and cover layer etc.
On the contrary, in the present invention, notice that in the combination on InGaN potential well layer and AlGaN barrier layer, they have the optimum value of greatly different crystal growth temperatures, and this is considered to a problem.Exactly, compare with GaN, the AlN that forms for AlGaN has high fusing point, and the InN that forms for AlGaN has the fusing point lower than GaN.Concrete optimum temperature for the crystal growth of GaN is 1000 ℃, for InGaN, is no more than 1000 ℃ (being preferably about 600-800 ℃), and for AlGaN, is not less than the concrete optimum temperature of the crystal growth of GaN.Therefore, for the combination on InGaN potential well layer and AlGaN barrier layer, the growth temperature that need greatly change potential well layer and barrier layer preferably is worth to it, so that the layer with preferred crystal quality to be provided.
But, need interruption of growth for the change of the growth temperature on each potential well layer/barrier layer.Be the thin potential well layer of about 3nm for thickness, the interruption of growth causes thickness owing to the etching action that produces during growth interruption, from the teeth outwards crystal defect etc. change.
Because this trade-off relation, be difficult to obtain high-quality product by the combination of AlGaN barrier layer and InGaN potential well layer.In addition, AlGaN as the barrier layer, is appeared at the problem of being out of shape on the potential well layer, this stops high output.
Therefore, among the present invention,, reduced above-mentioned trade-off problem by using the material of GaN as the barrier layer.This has reduced the difference of band gap between barrier layer and the potential well layer, and has improved two-layer crystal mass generally and improved output.
And, for the InGaN based material, the AlInGaN that obtains by mixing Al in InGaN can be used as potential well layer, can obtain thus and effect and effect identical in the situation of InGaN.
And, among the present invention, solution about the top described problem of the combination that relates to InGaN potential well layer and AlGaN barrier layer, recommend a kind of the embodiment that does not contain the AlGaN layer between crystal substrates and the potential well layer (in the embodiment of mentioning after a while, wherein the AlGaN basal layer is formed directly on the AlN low temperature-grown buffer layer between AlGaN basal layer and the potential well layer).This alleviates the problems referred to above that difference caused by crystal growth temperature.As a specific embodiments eliminating the AlGaN layer, can mention the embodiment of using GaN layer rather than AlGaN layer.In the example of Fig. 1, the undope unadulterated GaN crystal layer (thickness 0.1 μ m-2.0 μ m) of matter and the n-type GaN crystal layer (contact layer and cover layer) of growing thereon of growth on the GaN low temperature buffer layer.Can omit unadulterated GaN crystal layer.In addition, can give n-type GaN crystal layer different carrier concentrations, and can be individually formed and be n-type GaN contact layer and n-type GaN cover layer.
As the different preferred embodiments of MQW structure, can mention one wherein potential well layer be unadulterated and add the embodiment of Si to the barrier layer.
Figure 5 shows that the curve chart that concerns between the barrier layer carrier concentration that adopts the Si doping blocking layer and the radiative output.At the sample that is used for measuring, the number of plies of potential well layer be 6 and the thickness on barrier layer be 10nm, and this is applied to other situation equally.As being clear that from wherein curve under the unadulterated situation of Si, radiative output is little, and the amount that Si is mixed is not less than 5 * 10
18Cm
-3, radiative output reduces.Barrier layer doping Si suits, because it has improved photoemissive intensity.But when addition increased too much, degree of crystallinity descended, and the light emissive porwer reduces on the contrary.The Sq that Si mixes is 5 * 10
16Cm
-3-5 * 10
18Cm
-3
The crystal substrates that is used to grow can be any substrate, as long as can growing GaN be crystal.Preferred crystal substrates for example comprises, sapphire (C-plane, A-plane, R-plane), SiC (6H, 4H, 3C), GaN, AlN, Si, spinelle, ZnO, GaAs, NGO etc.In addition, substrate can contain these crystal as superficial layer.Do not limit the orientation of substrate especially, and it can also just be a kind of substrate or a kind of substrate with oblique angle (off angle).
As required, can form resilient coating between the crystal layer at crystal substrates and GaN.Will be by GaN, the substrate that AlN crystal etc. is made is as crystal substrates, and resilient coating is not necessarily.
Find that in order to obtain having the high-quality GaN film of dislocation still less etc., the AlGaN film (AlGaN basal layer) that preferably lattice constant is different from the GaN film is set to basal layer, with the growing GaN film.When growing GaN on the AlGaN film, on GaN, apply compression stress.When growing under this state, with respect to the curved dislocation (exactly, the commitment of growing GaN on the AlGaN film) vertically of the direction of growth in AlGaN film/GaN film interface, and dislocation is not propagated on the direction of growth.That is, can so obtain the high quality GaN film.For this AlGaN basal layer of growing, preferably resilient coating is used as the basis.As preferred resilient coating, can mention that GaN is a low temperature-grown buffer layer.By with reference to known technology, can know material, formation method and the formation condition of resilient coating.As for GaN is the material of low temperature-grown buffer layer, can mention GaN, AlN, and InN etc., and, can mention 300 ℃-600 ℃ for growth temperature.The thickness of preferred resilient coating is 10nm-50nm, is preferably 20nm-40nm especially.As particularly preferred pattern, can mention the AlN resilient coating.An example of the component structure of embodiment for this reason shown in Figure 2.As shown in this figure, on crystal substrates B, comprise the laminar structure S that GaN is a crystal layer, and on AlN low temperature-grown buffer layer 10, form Al by 10 growths of AlN low temperature-grown buffer layer
XGa
1-XN (0＜X≤1) basal layer 11.Al
XGa
1-XThe optimum thickness of N basal layer is formed (X value) according to Al and is changed.
For example, when Al consisted of 30% (X=0.3), preferred thickness was 10nm-5 μ m, was preferably 50nm-1 μ m especially.When it is thinner than 10nm, can not obtain effect recited above, this is not preferred.When it was thicker than 5 μ m, the degree of crystallinity of GaN layer did not preferably reduce.
In addition, Al
XGa
1-XThe Al of N basal layer forms (X value) can have gradient in the direction of growth.Al form can be continuously or multistage terrace land change.
When AlGaN basis bed thickness (for example, when Al consists of 30%, about 500nm-5000nm), can directly form luminous component thereon.
Among the present invention, the p-type contact layer that forms with InGaN is a kind of contact layer of preferred embodiment.
That is, in the conventional GaN based light-emitting device that uses p-type GaN contact layer, p-type contact resistance is up to 1 * 10
-3Ω cm
2Even, and for good be about 1 * 10
-4Ω cm
2On the contrary, when InGaN is used as the material of p-type contact layer, the benefit below obtaining: the acceptor level step-down, and hole concentration increases and contact resistance is reduced to about 1 * 10
-6Ω cm
2
The p-type contact layer that is preferably formed p-type electrode especially is the In that Mg mixes
YGa
1-YN (0＜Y≤1).Be set to N by the gaseous environment atmosphere during the InGaN layer growth
2+ NH
3, can make the activation condition gentleness that is called as the Mg of p-type activation processing after the growth maybe can omit processing itself.This is because of the H still less in growing period gaseous environment atmosphere
2Content can prevent to make the inactive H of Mg
2Be mixed in the film.And because the acceptor level that forms with Mg doping InGaN the time is low, hole concentration at room temperature uprises, and it makes the mild condition of p-type activation processing equally, maybe can omit processing itself.
By using p-type InGaN contact layer to ultraviolet emitting device, can improve radiative output biglyyer.This is that it comes from such fact because of the diffusion of impurity in potential well layer that can suppress to mix, and promptly owing to the front, can make condition (particularly heating anneal) gentleness of p-type activation processing, maybe can omit processing itself.
Especially, when being the potential well layer made of crystal by unadulterated GaN and being barrier layer that crystal is made when forming the MQW structure that heat treatment not necessarily by the GaN that Si mixes.Therefore, can obtain precipitous impurity profile.As a result, think the further radiative output that improved.
Grown GaN is the dislocation density of crystal layer on the crystal substrates in order to be reduced in, and can introduce the structure that is used to reduce dislocation density aptly.Following situation can appear, and will be by foreign material such as SiO
2Be contained in Deng the parts of making and contain in the laminar structure that GaN is a crystal layer, together with the introducing of the structure that is used to reduce dislocation density.
As for the structure that is used to reduce dislocation density, for example, can mention structure described below:
(a) a kind of wherein on crystal substrates with formation mask layers such as candy strip (use be SiO
2Deng) structure so that can carry out conventional known selective growth method (ELO method).
(b) a kind of to crystal substrates carried out point-like, striated recessed-structure of protruding processing so that GaN be crystal can lateral growth or grow towards (facet).
In the time of suitable, can merge these structures and resilient coating.
In the structure that is used for reducing dislocation density, above-mentioned (b) is a kind of structure that does not preferably have mask layer.This is explained as follows:
For recessed-protruding processing method, for example, that mentions has: a kind of comprise use conventional photoetching technique according to target recessed-protruding embodiment forms pattern, and use RIE technology etc. carry out etching and processing with obtain target recessed-method of male structure.
The configuration pattern of recessed-male structure for example comprises, a kind of pattern that comprises row's point-like female component (or convex part), a kind of striped that comprises the linear or shaped form recessed channel (or convex ridge) of settling or concentric pattern etc. with fixing interval or uncertain interval.The pattern that contains the convex ridge that clathrate intersects can be regarded as the pattern that point-like (square hole shape) female component by neat arrangement forms.For recessed-protruding section shape, can mention rectangle (comprising trapezoidal) ripple, triangular wave, sine curve etc.
In so various recessed-protruding embodiment, preferred wherein settle the striated of linear recessed channel (or convex ridge) recessed-convex pattern (square wave cross section) with fixing interval, reason is that it can simplify manufacturing step and form pattern easily.
When will form striated recessed-during convex pattern, vertical aspect of striped can be any direction.For will be by the embedding pattern Grown GaN be for the crystal,＜11-20〉direction suppresses the growth in the horizontal direction, it helps the inclined-plane again as the { formation on 1-101} plane etc.As a result, the dislocation that spreads at the C-direction of principal axis from substrate side to horizontal direction bending, and is not easy upwards diffusion on this plane, can be preferably formed the zone of low-dislocation-density thus especially.
When the longitudinal direction with striped be set at will Grown GaN be crystal＜1-100 during direction, from the upper part of projection begin Grown GaN be crystal at the lateral high-speed rapid growth, and to form the GaN that has as the female component in hole be crystal layer.Even the longitudinal direction of striped is set at＜1-100〉during direction, by the growth conditions that employing forms the plane easily, can obtain with by＜11-20 the identical effect that provides of direction.
Being used to make recessed-protruding cross section is that the preferred size of square wave is as follows: the preferable width of recessed channel: 0.1 μ m-20 μ m is preferably 0.5 μ m-10 μ m especially.The preferable width of bossing: 0.1 μ m-20 μ m is preferably 0.5 μ m-10 μ m especially.Recessed-protruding scope (degree of depth of recessed channel): be not less than 20% of wideer person in concave portions and the bossing.These sizes of Ji Suaning are identical with the recessed-male structure with different cross section shape with spacing etc. thus.
The GaN that can mention is that the growing method of crystal layer comprises for example HVPE, MOVPE, MBE etc.In order to form thick film, preferred HVPE, but in order to form film, preferred MOVPE and MBE.
Embodiment
In this embodiment, prepare ultraviolet leds shown in Figure 1, and be 10 nm and, obtain 25 kinds of samples altogether, the output of measuring each sample then the number of plies setting from 1 to 25 of potential well layer with the fixed thickness on barrier layer.The method that forms element is as follows:
For each sample, in the MOVPE device, settle C-plane sapphire substrate, and under hydrogen atmosphere, be heated to 1100 ℃ to carry out thermal etching.Temperature is reduced to 500 ℃, and by feeding as the trimethyl gallium (hereinafter referred to as TMG) of III-th family composition material with as the ammonia of N composition material, the thick GaN low temperature buffer layer of growth 30nm.
Temperature is increased to 1000 ℃ then, and feeds TMG and ammonia, with the thick unadulterated GaN crystal layer 1 of the 2 μ m that grow as composition material.Then, feed SiH
4With the thick Si doped n-type GaN crystal layer of the 3 μ m that grow (contact and cover layer).
[quantum potential well structure]
For each sample, temperature is reduced to 800 ℃, and (thickness 10nm is added with 5 * 10 with the GaN barrier layer
17Cm
-3Si) and the logarithm of InGaN potential well layer (radiative wavelength is 380nm, and In consists of 0.03, and thickness is 3nm) change to 25 from 1.And, in each sample, form the last GaN barrier layer adjacent and (be doped with Si (5 * 10 with the p-layer
17Cm
-3), thickness 20nm).
For every kind of sample, growth temperature is increased to 1000 ℃, form the thick p-type GaN contact layer of thick p-type AlGaN cover layer 4 of 30nm and 50nm in succession, to obtain the ultraviolet leds wafer that radiative wavelength is 380nm, then form electrode, and cutting element, the ultraviolet leds chip obtained.
The ultraviolet leds chip sample with different number of plies potential well layers that obtains is above excited with 20mA under the bare chip state, and the output of measurement under the 380nm wavelength.As a result, as shown in Figure 3, obtain showing the curve chart of relation between the potential well layer number of plies and the output.According to top described, the number of plies of potential well layer should be 2-20, and it provides the output that is not less than 2mW.Find that the number of plies of preferred especially potential well layer is 6 to 15, it provides the radiative output that is not less than 5mW.
In this embodiment, preparing ultraviolet leds shown in Figure 1, the number of plies of potential well layer is fixed as 6, and the thickness that forms the barrier layer then, is measured the output of each sample from the sample that 3nm changes to 40nm with the foregoing description 1 similar method.
The ultraviolet leds chip sample with different blocking layer thickness that obtains among this embodiment is excited with 20mA under the bare chip state, and the output of measurement under the 380nm wavelength.As a result, as shown in Figure 4, obtain showing the curve chart of relation between barrier layer thickness and the output.According to top described, the thickness on barrier layer should be 7nm-30nm, and it provides the output that is not less than 2mW.Find that the thickness on preferred especially barrier layer is 8nm-15nm, it provides the radiative output that is not less than 5mW.
Among the described in the above embodiment 1, be a kind of, among the described embodiment 2, be fixed as the number of plies of potential well layer a kind of in the above the fixed thickness that stops layer.With with the identical mode of element formation method recited above, the sample that the thickness that preparation wherein stops layer changes in the 7-30nm scope and the number of plies of potential well layer changes in the scope at 2-20 under each thickness.Find, in such element sample,, under any thickness on barrier layer, obtain with Fig. 3 similar curve, and, under any number of plies of potential well layer, obtain with Fig. 4 similar curve according to the variation of barrier layer thickness according to the variation of the potential well layer number of plies.
In this embodiment, in all samples of described in the above embodiment 1 and 2 preparations, prepare the ultraviolet leds sample by following method: use the AlN low temperature buffer layer to replace the GaN low temperature buffer layer, use the AlGaN basal layer to replace unadulterated GaN crystal layer and use p-type InGaN contact layer to replace p-type GaN contact layer.Measure the output of each sample.The method that forms element is as follows.
In each sample, in the MOVPE device, settle C-plane sapphire substrate, and under hydrogen atmosphere, be heated to 1100 ℃ to carry out thermal etching.Temperature is reduced to 350 ℃, and feeds as the trimethyl aluminium (hereinafter referred to as TMA) of III-th family composition material with as the ammonia of N composition material, the thick AlN low temperature buffer layer of growth 20nm.
Then, temperature is increased to 1000 ℃, and feeds TMA, TMG and ammonia as composition material, the unadulterated AlGaN crystal layer (basal layer) 1 so that the thick Al of growth 200nm consists of 10% then, stops the supply of TMA, and feeds SiH
4With the thick Si doped n-type GaN crystal layer of the 4 μ m that grow (contact and cover layer).Then, form the MQW structure with the method identical with embodiment 1 and 2.
For every kind of sample, growth temperature is increased to 1000 ℃, form the thick p-type AlGaN resilient coating 4 of 30nm in succession, the p-type InGaN contact layer (In consists of 10%) that p-type GaN layer that 50nm is thick and 5nm are thick, to obtain the ultraviolet leds wafer that radiative wavelength is 380nm, then form electrode, and cutting element, the ultraviolet leds chip obtained.
The ultraviolet leds chip sample that obtains is above excited with 20mA under the bare chip state, and the output of measurement under the 380nm wavelength.As a result, compare with 2 sample with embodiment 1, the output of each sample has improved about 10%-30%.
Industrial usability
As mentioned above, for the MQW structure, the number of plies by potential well layer is set to 2-20 and makes The thickness on barrier layer is 7nm-30nm, by using InGaN based material, particularly InGaN as the ultraviolet light element of luminescent layer material, can obtain conventional inaccessiable high output.
This application is based on the patent application 350615/2001 and 073871/2002 that Japan submits to, and its content is combined in this by reference.
Claims (10)
1. ultraviolet emitting device, its be a kind of have comprise crystal substrates and GaN is the GaN based semiconductor light-emitting device of the laminar structure of crystal layer, described GaN is that crystal layer is formed directly into or is formed on the described substrate by resilient coating, wherein said laminar structure comprises the luminous component that contains p-type layer and n-type layer, wherein said luminous component has a plurality of quantum potential well structures, and described potential well layer is to be made by the InGaN based material that can launch ultraviolet light, the number of plies of described potential well layer is 2-20, and the thickness on described barrier layer is 7nm-30nm.
2. ultraviolet emitting device according to claim 1, laminar structure wherein recited above forms on crystal substrates by the AlN low temperature-grown buffer layer, wherein directly forms Al on described AlN low temperature-grown buffer layer
XGa
1-XN (0＜X≤1) basal layer.
3. ultraviolet emitting device according to claim 2, it is at described Al
XGa
1-XThe layer of not making between N (0＜X≤1) basal layer and the described potential well layer by AlGaN.
4. ultraviolet emitting device according to claim 1, the p-type layer in the wherein described in the above laminar structure and the position of n-type layer relation be p-type layer at upside, and p-type contact layer is by In
YGa
1-YN (0＜Y≤1) makes.
5. ultraviolet emitting device according to claim 1, a plurality of quantum potential well structures wherein recited above have the barrier layer that contacts with p-type layer, and the thickness on the described barrier layer that contacts with p-type layer is 10nm-30nm.
6. it is that the potential well layer made of crystal and the GaN that mixed by Si are the barrier layer that crystal is made that ultraviolet emitting device according to claim 1, a plurality of quantum potential well structures wherein recited above comprise by unadulterated GaN.
7. ultraviolet emitting device according to claim 1, a plurality of quantum potential well structures wherein recited above comprise by In
XGa
1-XPotential well layer that N (0＜X≤1) makes and the barrier layer of making by GaN.
8. ultraviolet emitting device according to claim 7, In wherein recited above
XGa
1-XIt is 0＜X≤0.11 that In among the N forms X.
9. ultraviolet emitting device according to claim 1, the layer that it is not made by AlGaN between described crystal substrates and described potential well layer.
10. ultraviolet emitting device according to claim 1 wherein carries out recessed-protruding processing in its surface with described crystal substrates, and vapor phase growth GaN be crystal layer cover described recessed-convex portion is with the cambium layer laminated structure.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001350615 | 2001-11-15 | ||
| JP350615/2001 | 2001-11-15 | ||
| JP2002073871A JP2003218396A (en) | 2001-11-15 | 2002-03-18 | UV light emitting element |
| JP73871/2002 | 2002-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1586015A true CN1586015A (en) | 2005-02-23 |
| CN100355094C CN100355094C (en) | 2007-12-12 |
Family
ID=26624542
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028225341A Expired - Lifetime CN100355094C (en) | 2001-11-15 | 2002-11-12 | Ultraviolet emitting device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2003218396A (en) |
| KR (1) | KR100709058B1 (en) |
| CN (1) | CN100355094C (en) |
| TW (1) | TW567620B (en) |
| WO (1) | WO2003043097A1 (en) |
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| CN103748697A (en) * | 2011-08-08 | 2014-04-23 | 日进Led有限公司 | Nitride semiconductor light-emitting element having superior leakage current blocking effect and method for manufacturing same |
| CN104157754A (en) * | 2014-07-03 | 2014-11-19 | 华南理工大学 | InGaN/GaN multiple quantum well growing on W substrate and preparation method thereof |
| CN104518059A (en) * | 2014-11-06 | 2015-04-15 | 聚灿光电科技(苏州)有限公司 | Epitaxy structure and growth method thereof based on GaN-based quantum well |
| CN110581439A (en) * | 2018-06-01 | 2019-12-17 | 全新光电科技股份有限公司 | Laser Diodes with Defect Barriers |
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| JP2008124060A (en) * | 2006-11-08 | 2008-05-29 | Showa Denko Kk | Method for producing group III nitride compound semiconductor light emitting device, group III nitride compound semiconductor light emitting device, and lamp |
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| JP2008177525A (en) * | 2006-12-20 | 2008-07-31 | Showa Denko Kk | Group III nitride semiconductor light emitting device manufacturing method, group III nitride semiconductor light emitting device, and lamp |
| JP2008198705A (en) * | 2007-02-09 | 2008-08-28 | Showa Denko Kk | Method for manufacturing group iii nitride semiconductor light-emitting device, group iii nitride semiconductor light-emitting device, and lamp |
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| JPH08111558A (en) * | 1994-10-07 | 1996-04-30 | Hitachi Ltd | Semiconductor laser element |
| EP0732754B1 (en) * | 1995-03-17 | 2007-10-31 | Toyoda Gosei Co., Ltd. | Light-emitting semiconductor device using group III nitride compound |
| JPH0936423A (en) * | 1995-07-24 | 1997-02-07 | Toyoda Gosei Co Ltd | Group iii nitride semiconductor light emitting element |
| JP3778609B2 (en) * | 1996-04-26 | 2006-05-24 | 三洋電機株式会社 | Manufacturing method of semiconductor device |
| JP3471685B2 (en) * | 1999-03-17 | 2003-12-02 | 三菱電線工業株式会社 | Semiconductor substrate and manufacturing method thereof |
| JP3460641B2 (en) * | 1999-09-28 | 2003-10-27 | 日亜化学工業株式会社 | Nitride semiconductor device |
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-
2002
- 2002-03-18 JP JP2002073871A patent/JP2003218396A/en active Pending
- 2002-11-12 CN CNB028225341A patent/CN100355094C/en not_active Expired - Lifetime
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104157754A (en) * | 2014-07-03 | 2014-11-19 | 华南理工大学 | InGaN/GaN multiple quantum well growing on W substrate and preparation method thereof |
| CN104157754B (en) * | 2014-07-03 | 2017-01-11 | 华南理工大学 | InGaN/GaN multiple quantum well growing on W substrate and preparation method thereof |
| CN104518059A (en) * | 2014-11-06 | 2015-04-15 | 聚灿光电科技(苏州)有限公司 | Epitaxy structure and growth method thereof based on GaN-based quantum well |
| CN110581439A (en) * | 2018-06-01 | 2019-12-17 | 全新光电科技股份有限公司 | Laser Diodes with Defect Barriers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003218396A (en) | 2003-07-31 |
| WO2003043097A1 (en) | 2003-05-22 |
| TW200300300A (en) | 2003-05-16 |
| TW567620B (en) | 2003-12-21 |
| KR100709058B1 (en) | 2007-04-18 |
| CN100355094C (en) | 2007-12-12 |
| KR20040062636A (en) | 2004-07-07 |
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Address after: Tokyo, Japan Patentee after: Mitsubishi Cable Industries, Ltd. Address before: Tokyo Electron Limited Patentee before: Mitsubishi Cable Industries, Ltd. |
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Effective date of registration: 20081010 Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: Mitsubishi Cable Industries, Ltd. |
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Effective date of registration: 20160407 Address after: Japan's Aichi Patentee after: Toyoda Gosei Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI CHEMICAL Corp. |
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Granted publication date: 20071212 |
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