CN109545923A - A kind of green light LED epitaxial wafer and preparation method thereof - Google Patents
A kind of green light LED epitaxial wafer and preparation method thereof Download PDFInfo
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 29
- 235000012431 wafers Nutrition 0.000 description 27
- 229910002601 GaN Inorganic materials 0.000 description 26
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- 239000002019 doping agent Substances 0.000 description 5
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Classifications
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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
- 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]
- H10H20/01—Manufacture or treatment
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Abstract
本发明公开了一种绿光发光二极管外延片及其制作方法，属于半导体技术领域。所述绿光发光二极管外延片包括衬底、N型半导体层、有源层和P型半导体层，所述N型半导体层、所述有源层和所述P型半导体层依次层叠在所述衬底上；所述有源层包括多个量子阱和多个量子垒，所述多个量子阱和所述多个量子垒交替层叠设置；所述量子阱的材料采用未掺杂的MoS2，所述量子垒的材料采用未掺杂的InxAl1‑xN，0＜x＜0.3。本发明通过采用未掺杂的MoS2作为量子阱的材料，同时采用未掺杂的InxAl1‑xN作为量子垒的材料，0＜x＜0.3，InxAl1‑xN和MoS2之间的晶格匹配较好，可以有效缓解LED的极化效应。
The invention discloses a green light emitting diode epitaxial wafer and a manufacturing method thereof, belonging to the technical field of semiconductors. The green light emitting diode epitaxial wafer includes a substrate, an N-type semiconductor layer, an active layer and a P-type semiconductor layer, and the N-type semiconductor layer, the active layer and the P-type semiconductor layer are sequentially stacked on the on the substrate; the active layer includes a plurality of quantum wells and a plurality of quantum barriers, and the plurality of quantum wells and the plurality of quantum barriers are alternately stacked; the material of the quantum wells is undoped MoS 2 , the material of the quantum barrier adopts undoped In x Al 1-x N, 0<x<0.3. The present invention adopts undoped MoS 2 as the material of the quantum well, and simultaneously uses the undoped In x Al 1-x N as the material of the quantum barrier, 0<x<0.3, In x Al 1-x N and MoS The lattice matching between 2 is good, which can effectively alleviate the polarization effect of the LED.
Description
Technical field
The present invention relates to technical field of semiconductors, in particular to a kind of green light LED epitaxial wafer and its production side
Method.
Background technique
Light emitting diode (English: Light Emitting Diode, referred to as: LED) it is a kind of semi-conductor electricity that can be luminous
Subcomponent.Gallium nitride (GaN) has good thermal conductivity, while having the good characteristics such as high temperature resistant, acid and alkali-resistance, high rigidity,
Gallium nitride (GaN) base LED is set to receive more and more attention and study.
Epitaxial wafer is the primary finished product in LED preparation process.Existing GaN-based LED epitaxial wafer includes substrate, N-type half
Conductor layer, active layer and p type semiconductor layer, n type semiconductor layer, active layer and p type semiconductor layer stack gradually on substrate.Lining
Bottom is used to provide growing surface for epitaxial material, and n type semiconductor layer is used to provide the electronics for carrying out recombination luminescence, P-type semiconductor
Layer carries out the hole of recombination luminescence for providing, and the radiation recombination that active layer is used to carry out electrons and holes shines.
In the implementation of the present invention, the inventor finds that the existing technology has at least the following problems:
The material of Quantum Well generally selects InGaN, and the material that quantum is built generally selects gallium nitride.For issuing green light
For the active layer of (wavelength is 500nm~580nm), the content of indium component is very high in Quantum Well, between Quantum Well and quantum base
Lattice mismatch it is very serious, cause the polarity effect of LED to increase, be easy to cause the ageing failure of LED, reduce device use the longevity
Life.
Summary of the invention
The embodiment of the invention provides a kind of green light LED epitaxial wafers and preparation method thereof, are able to solve existing skill
The larger problem of lattice mismatch between art Quantum Well and quantum base.The technical solution is as follows:
On the one hand, the embodiment of the invention provides a kind of green light LED epitaxial wafer, the green light LEDs
Epitaxial wafer includes substrate, n type semiconductor layer, active layer and p type semiconductor layer, the n type semiconductor layer, the active layer and institute
P type semiconductor layer is stated to stack gradually over the substrate；The active layer includes that multiple Quantum Well and multiple quantum are built, described more
A Quantum Well and the multiple quantum build alternately laminated setting；The material of the Quantum Well uses undoped MoS2, the amount
The material that son is built uses undoped InxAl1-xN, 0 < x < 0.3.
Optionally, the quantity that the quantum is built is identical with the quantity of the Quantum Well, the quantity of the Quantum Well for 3~
8.
Optionally, the Quantum Well with a thickness of 1nm~2nm.
Optionally, the quantum build with a thickness of 10nm~15nm.
Optionally, the green light LED epitaxial wafer further includes electronic barrier layer, and the electronic barrier layer setting exists
Between the active layer and the p type semiconductor layer；The electronic barrier layer includes multiple first sublayers and multiple second sublayers,
The multiple first sublayer and the multiple alternately laminated setting of second sublayer；The material of first sublayer is adulterated using p-type
AlyGa1-yThe material of N, 0.05 < y < 0.2, second sublayer use the doped or undoped In of p-typezGa1-zN, 0.1 < z
< 0.5.
On the other hand, the embodiment of the invention provides a kind of production method of green light LED epitaxial wafer, the systems
Include: as method
One substrate is provided；
N type semiconductor layer, active layer and p type semiconductor layer are successively grown over the substrate；
Wherein, the active layer includes that multiple Quantum Well and multiple quantum are built, the multiple Quantum Well and the multiple amount
Son builds alternately laminated setting；The material of the Quantum Well uses undoped MoS2, the material that the quantum is built is using undoped
InxAl1-xN, 0 < x < 0.3.
Optionally, the growth temperature of the Quantum Well is 600 DEG C~700 DEG C.
Optionally, the growth temperature that the quantum is built is 500 DEG C~600 DEG C.
Optionally, the growth pressure that the quantum is built is identical as the growth pressure of the Quantum Well.
Preferably, the growth pressure of the active layer is 200torr~500torr.
Technical solution provided in an embodiment of the present invention has the benefit that
Using undoped MoS2As the material of Quantum Well, while using undoped InxAl1-xN is built as quantum
Material, 0 < x < 0.3, by adulterating In in AlN, by InxAl1-xThe forbidden bandwidth of N is reduced to GaN's from the 6.2eV of AlN
3.2eV, it is consistent with the forbidden bandwidth of existing quantum barrier material, and MoS2Forbidden bandwidth be 2.15eV, MoS2And InxAl1-xN it
Between have energy level difference, electrons and holes can be by InxAl1-xN is strapped in MoS2Middle recombination luminescence.According between wavelength and forbidden bandwidth
Corresponding relationship (wavelength=1240/ forbidden bandwidth), MoS2The wavelength to emit beam uses not in the wave-length coverage of green light
The MoS of doping2As the material of Quantum Well, while using undoped InxAl1-xThe material that N is built as quantum, 0 < x < 0.3,
The sending of green light may be implemented.And as 0 < x < 0.3, InxAl1-xN and MoS2Between Lattice Matching it is preferable, on the one hand may be used
The polarity effect of LED is effectively relieved, LED failure caused by polarizing is reduced, the service life of device is promoted；On the other hand may be used also
To reduce the stress and defect of lattice mismatch generation, the migration rate of carrier is improved, the recombination luminescence efficiency of active layer is promoted,
Reduce photon loss, the final luminous efficiency for improving LED.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is a kind of structural schematic diagram of green light LED epitaxial wafer provided in an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of active layer provided in an embodiment of the present invention；
Fig. 3 is a kind of flow chart of the production method of green light LED epitaxial wafer provided in an embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
The embodiment of the invention provides a kind of green light LED epitaxial wafers.Fig. 1 is provided in an embodiment of the present invention one
The structural schematic diagram of kind green light LED epitaxial wafer.Referring to Fig. 1, which includes substrate 10, N
Type semiconductor layer 20, active layer 30 and p type semiconductor layer 40, n type semiconductor layer 20, active layer 30 and p type semiconductor layer 40 according to
It is secondary to be layered on substrate 10.
Fig. 2 is the structural schematic diagram of active layer provided in an embodiment of the present invention.Referring to fig. 2, active layer 30 includes multiple amounts
Sub- trap 31 and multiple quantum build 32, and multiple Quantum Well 31 and multiple quantum build 32 alternately laminated settings.The material of Quantum Well 31 is adopted
With undoped MoS2, the material at quantum base 32 is using undoped InxAl1-xN, 0 < x < 0.3 (preferably 0.15).
The embodiment of the present invention uses undoped MoS2As the material of Quantum Well, while using undoped InxAl1-xN
As the material that quantum is built, 0 < x < 0.3, by adulterating In in AlN, by InxAl1-x6.2eV of the forbidden bandwidth of N from AlN
It is reduced to the 3.2eV of GaN, it is consistent with the forbidden bandwidth of existing quantum barrier material, and MoS2Forbidden bandwidth be 2.15eV, MoS2
And InxAl1-xThere is energy level difference between N, electrons and holes can be by InxAl1-xN is strapped in MoS2Middle recombination luminescence.According to wavelength and taboo
Corresponding relationship (wavelength=1240/ forbidden bandwidth) between bandwidth, MoS2Wave-length coverage of the wavelength to emit beam in green light
It is interior, therefore use undoped MoS2As the material of Quantum Well, while using undoped InxAl1-xThe material that N is built as quantum
The sending of green light may be implemented in material, 0 < x < 0.3.And as 0 < x < 0.3, InxAl1-xN and MoS2Between Lattice Matching
Preferably, the polarity effect of LED on the one hand can be effectively relieved, reduce LED failure caused by polarizing, promote device uses the longevity
Life；On the other hand the stress and defect that can also reduce lattice mismatch generation, improve the migration rate of carrier, promote active layer
Recombination luminescence efficiency, reduce photon loss, the final luminous efficiency for improving LED.
And it is provided in an embodiment of the present invention using undoped MoS2As the material of Quantum Well, while using undoped
InxAl1-xThe material that N is built as quantum, 0 < x < 0.3, the Lattice Matching effect between Quantum Well and quantum base is fairly good,
Completely without stress release layer is arranged before active layer, simplifies and realize, reduce cost.
Optionally, the quantity at quantum base 32 is identical as the quantity of Quantum Well 31, and the quantity of Quantum Well 31 can be 3~8
It is a.
If the quantity that Quantum Well and quantum are built is less than 3, may due to negligible amounts that Quantum Well and quantum are built and
Make electrons and holes be unable to fully carry out recombination luminescence, reduces the luminous efficiency of LED；If the quantity that Quantum Well and quantum are built is more
A 8, then the compound of electrons and holes may be influenced since the quantity of Quantum Well and quantum base is more, can also reduce LED
Luminous efficiency.
Optionally, the thickness of Quantum Well 31 can be 1nm~2nm.
If the thickness of Quantum Well be less than 1nm, may it is relatively thin due to Quantum Well and make electrons and holes be unable to fully into
Row recombination luminescence reduces the luminous efficiency of LED；If the thickness of Quantum Well is greater than 2nm, may be led since Quantum Well is thicker
It causes electrons and holes to concentrate on individual Quantum Well and carries out recombination luminescence, influence whole luminous efficiency.
Optionally, the thickness that quantum builds 32 can be 10nm~15nm.
If the thickness that quantum is built is less than 10nm, it may be built relatively thin and electrons and holes can not be limited in due to quantum
Recombination luminescence is carried out in Quantum Well, influences the luminous efficiency of LED；It, may be due to amount if the thickness that quantum is built is greater than 15nm
Son builds migration that is thicker and influencing electrons and holes, reduces the luminous efficiency of LED.
Specifically, the material of substrate 10 can use sapphire (main material is aluminum oxide), as crystal orientation is
[0001] sapphire.The material of n type semiconductor layer 20 can use the gallium nitride of n-type doping (such as silicon).P type semiconductor layer 40
Material can using p-type doping (such as magnesium) gallium nitride.
Further, the thickness of n type semiconductor layer 20 can be 1 μm~5 μm, preferably 3 μm；N in n type semiconductor layer 20
The doping concentration of type dopant can be 1018cm-3~1019cm-3, preferably 5*1018cm-3.The thickness of p type semiconductor layer 40 can
Think 100nm~800nm, preferably 450nm；The doping concentration of P-type dopant can be 10 in p type semiconductor layer 4018/cm3
~1020/cm3, preferably 1019/cm3。
In practical applications, it can be equipped with graphical silicon dioxide layer on substrate 10, on the one hand reduce GaN epitaxy material
On the other hand dislocation density changes the shooting angle of light, improves the extraction efficiency of light.Specifically, it can first be served as a contrast in sapphire
Layer of silicon dioxide material is laid on bottom；Form the photoresist of certain figure on earth silicon material using photoetching technique again；
Then the earth silicon material of not photoresist overlay, the earth silicon material formation figure left are removed using dry etching technology
Shape silicon dioxide layer；Finally remove photoresist.
Optionally, as shown in Figure 1, the green light LED epitaxial wafer can also include buffer layer 51, buffer layer 51 is set
Set between substrate 10 and n type semiconductor layer 20, with alleviate stress that lattice mismatch between substrate material and gallium nitride generates and
Defect, and nuclearing centre is provided for gallium nitride material epitaxial growth.
Specifically, the material of buffer layer 51 can use gallium nitride.
Further, the thickness of buffer layer 51 can be 15nm~35nm, preferably 25nm.
Preferably, as shown in Figure 1, the green light LED epitaxial wafer can also include undoped gallium nitride layer 52, not
Doped gallium nitride layer 52 is arranged between buffer layer 51 and n type semiconductor layer 20, further to alleviate substrate material and gallium nitride
Between lattice mismatch generate stress and defect, provide crystal quality preferable growing surface for epitaxial wafer main structure.
In specific implementation, buffer layer is the gallium nitride of the layer of low-temperature epitaxy first in patterned substrate, because
This is also referred to as low temperature buffer layer.The longitudinal growth for carrying out gallium nitride in low temperature buffer layer again, will form multiple mutually independent three
Island structure is tieed up, referred to as three-dimensional nucleating layer；Then it is carried out between each three-dimensional island structure on all three-dimensional island structures
The cross growth of gallium nitride forms two-dimension plane structure, referred to as two-dimentional retrieving layer；The finally high growth temperature one on two-dimensional growth layer
The thicker gallium nitride of layer, referred to as intrinsic gallium nitride layer.By three-dimensional nucleating layer, two-dimentional retrieving layer and intrinsic gallium nitride in the present embodiment
Layer is referred to as undoped gallium nitride layer.
Further, the thickness of undoped gallium nitride layer 52 can be 1 μm~5 μm, preferably 3 μm.
Optionally, as shown in Figure 1, the green light LED epitaxial wafer can also include electronic barrier layer 61, electronics resistance
Barrier 61 be arranged between active layer 30 and p type semiconductor layer 40, to avoid electron transition into p type semiconductor layer with hole into
Row non-radiative recombination reduces the luminous efficiency of LED.
Preferably, electronic barrier layer 61 may include multiple first sublayers and multiple second sublayers, multiple first sublayers and
Multiple alternately laminated settings of second sublayer.The material of first sublayer can be using the Al of p-type dopingyGa1-yN, 0.05 < y <
0.2, the material of the second sublayer uses the doped or undoped In of p-typezGa1-zN, 0.1 < z < 0.5.The potential barrier of AlGaN compared with
The potential barrier of height, InGaN is lower, and AlGaN and InGaN are alternately laminated, forms the alternate potential barrier of height, the blocking effect of electronics compared with
It is good.And AlyGa1-yN and InzGa1-zLattice match between N is preferable.
Further, the thickness of electronic barrier layer 61 can be 50nm~150nm, preferably 100nm.
Preferably, as shown in Figure 1, the green light LED epitaxial wafer can also include low temperature P-type layer 62, low temperature p-type
Layer 62 is arranged between active layer 30 and electronic barrier layer 61, causes active layer to avoid the higher growth temperature of electronic barrier layer
In phosphide atom be precipitated, influence the luminous efficiency of light emitting diode.
Specifically, the material of low temperature P-type layer 62 can be identical as the material of p type semiconductor layer 40.In the present embodiment,
The material of low temperature P-type layer 62 can be the gallium nitride of p-type doping.
Further, the thickness of low temperature P-type layer 62 can be 10nm~50nm, preferably 30nm；P in low temperature P-type layer 62
The doping concentration of type dopant can be 1018/cm3~1020/cm3, preferably 1019/cm3。
Optionally, as shown in Figure 1, the green light LED epitaxial wafer can also include contact layer 70, contact layer 70 is set
It sets on p type semiconductor layer 40, to form ohm between the electrode or transparent conductive film that are formed in chip fabrication technique
Contact.
Specifically, the material of contact layer 70 can be using the InGaN or gallium nitride of p-type doping.
Further, the thickness of contact layer 70 can be 5nm~300nm, preferably 100nm；P-type is adulterated in contact layer 70
The doping concentration of agent can be 1021/cm3~1022/cm3, preferably 5*1021/cm3。
The embodiment of the invention provides a kind of production methods of green light LED epitaxial wafer, are suitable for production Fig. 1 institute
The green light LED epitaxial wafer shown.Fig. 3 is a kind of system of green light LED epitaxial wafer provided in an embodiment of the present invention
Make the flow chart of method.Referring to Fig. 3, which includes:
Step 201: a substrate is provided.
Optionally, which may include:
Controlled at 1000 DEG C~1200 DEG C (preferably 1100 DEG C), in hydrogen atmosphere to substrate carry out 6 minutes~
It makes annealing treatment within 10 minutes (preferably 8 minutes)；
Nitrogen treatment is carried out to substrate.
The surface for cleaning substrate through the above steps avoids being conducive to the life for improving epitaxial wafer in impurity incorporation epitaxial wafer
Long quality.
Step 202: successively growing n type semiconductor layer, active layer and p type semiconductor layer on substrate.
In the present embodiment, active layer includes that multiple Quantum Well and multiple quantum are built, and multiple Quantum Well and multiple quantum are built
Alternately laminated setting；The material of Quantum Well uses undoped MoS2, the material that quantum is built is using undoped InxAl1-xN, 0 <
X < 0.3.
Optionally, the growth temperature of Quantum Well can be 600 DEG C~700 DEG C, be conducive to MoS2Growth.
Optionally, the growth temperature that quantum is built can be 500 DEG C~600 DEG C, can be to avoid InxAl1-xIn parsing in N.
Optionally, the growth pressure that quantum is built can be identical with the growth pressure of Quantum Well, facilitates realization.
Preferably, the growth pressure of active layer can be 200torr~500torr, and the crystal quality of active layer is preferable.
Specifically, which may include:
The first step, controlled at 1000 DEG C~1200 DEG C (preferably 1100 DEG C), pressure is 100torr~500torr
(preferably 300torr), grows n type semiconductor layer on substrate；
Second step grows active layer on n type semiconductor layer；
Third step, controlled at 850 DEG C~1080 DEG C (preferably 960 DEG C), pressure is that 100torr~300torr is (excellent
It is selected as 200torr), the growing P-type semiconductor layer on active layer.
Optionally, before the first step, which can also include:
Grown buffer layer on substrate.
Correspondingly, n type semiconductor layer is grown on the buffer layer.
Specifically, grown buffer layer on substrate may include:
Controlled at 400 DEG C~600 DEG C (preferably 500 DEG C), pressure be 400torr~600torr (preferably
500torr), grown buffer layer on substrate；
Controlled at 1000 DEG C~1200 DEG C (preferably 1100 DEG C), pressure be 400torr~600torr (preferably
500torr), the in-situ annealing carried out 5 minutes~10 minutes (preferably 8 minutes) to buffer layer is handled.
Preferably, on substrate after grown buffer layer, which can also include:
Undoped gallium nitride layer is grown on the buffer layer.
Correspondingly, n type semiconductor layer is grown on undoped gallium nitride layer.
Specifically, undoped gallium nitride layer is grown on the buffer layer, may include:
Controlled at 1000 DEG C~1100 DEG C (preferably 1050 DEG C), pressure be 100torr~500torr (preferably
300torr), undoped gallium nitride layer is grown on the buffer layer.
Optionally, before third step, which can also include:
Electronic barrier layer is grown on active layer.
Correspondingly, p type semiconductor layer is grown on electronic barrier layer.
Specifically, electronic barrier layer is grown on active layer, may include:
Controlled at 850 DEG C~1080 DEG C (preferably 960 DEG C), pressure be 200torr~500torr (preferably
350torr), electronic barrier layer is grown on active layer.
Preferably, before growing electronic barrier layer on active layer, which can also include:
The growing low temperature P-type layer on active layer.
Correspondingly, electronic barrier layer is grown in low temperature P-type layer.
Specifically, the growing low temperature P-type layer on active layer may include:
Controlled at 600 DEG C~850 DEG C (preferably 750 DEG C), pressure be 100torr~600torr (preferably
300torr), the growing low temperature P-type layer on active layer.
Optionally, after third step, which can also include:
Contact layer is grown on p type semiconductor layer.
Specifically, contact layer is grown on p type semiconductor layer, may include:
Controlled at 850 DEG C~1050 DEG C (preferably 950 DEG C), pressure be 100torr~300torr (preferably
200torr), contact layer is grown on p type semiconductor layer.
It should be noted that after above-mentioned epitaxial growth terminates, can first by temperature be reduced to 650 DEG C~850 DEG C (preferably
It is 750 DEG C), the annealing of 5 minutes~15 minutes (preferably 10 minutes) is carried out to epitaxial wafer in nitrogen atmosphere, then again
The temperature of epitaxial wafer is reduced to room temperature.
Control temperature, pressure each mean temperature, pressure in the reaction chamber of control growth epitaxial wafer, and specially metal is organic
Compound chemical gaseous phase deposition (English: Metal-organic Chemical Vapor Deposition, referred to as: MOCVD) set
Standby reaction chamber.Using trimethyl gallium or triethyl-gallium as gallium source when realization, high-purity ammonia is as nitrogen source, and trimethyl indium is as indium
Source, trimethyl aluminium select silicon as sulphur source, N type dopant as molybdenum source, di-t-butyl sulfide as silicon source, hexacarbonylmolybdenum
Alkane, P-type dopant select two luxuriant magnesium.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
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