CN105679898A - LED epitaxial structure with warpage adjusting structure layer and growth method thereof - Google Patents
LED epitaxial structure with warpage adjusting structure layer and growth method thereof Download PDFInfo
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- CN105679898A CN105679898A CN201610047614.4A CN201610047614A CN105679898A CN 105679898 A CN105679898 A CN 105679898A CN 201610047614 A CN201610047614 A CN 201610047614A CN 105679898 A CN105679898 A CN 105679898A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 30
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052594 sapphire Inorganic materials 0.000 claims description 11
- 239000010980 sapphire Substances 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 230000026267 regulation of growth Effects 0.000 claims description 4
- 230000007704 transition Effects 0.000 abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 3
- 229940095676 wafer product Drugs 0.000 abstract description 2
- 125000002950 monocyclic group Chemical group 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 206010020880 Hypertrophy Diseases 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Abstract
The invention relates to an LED epitaxial structure with a warpage adjusting structure layer and a growth method thereof. The warpage adjusting structure layer is inserted between a high-temperature GaN layer and a high-temperature N-type GaN layer of an LED. The structure is an Si3N4/GaN/AlGaN/GaN superlattice layer, the periodic number of the structure is 1-40, the monocyclic thickness is 31-1930 nm, the growth temperature is 700-1200 DEG C, and the growth pressure is 50-200 torr, wherein the growth conditions of an Si3N4 layer and an AlGaN layer can be the same and can also be different; when the growth conditions of the Si3N4 layer and the AlGaN layer are different, coordination is carried out to adjust the warpage degree in the growth process of the epitaxial wafer by changing the transition condition of a middle GaN layer and adjusting the thickness of the Si3N4 layer, the flow rate of SiH4, the thickness of the AlGaN layer and Al component, so that the on-chip parameter uniformity of LED epitaxial wafer product single-chips is improved, and the yield of the LED epitaxial wafer is improved.
Description
Technical field
The present invention relates to a kind of epitaxial structures growth method of LEDLED (photodiode) for the growth regulation good rate of warpage degree improving product, belong to LED preparing technical field.
Background technology
Wide bandgap semiconductor is the third generation semiconductor material after silicon and gallium arsenide, more and more it is subject to people's attention in recent years, that extensively studies at present mainly contains iii-v and II-VI compound semiconductor materials, silicon carbide (SiC) and diamond thin etc., obtains a wide range of applications in blue green light, ultraviolet leds, LD, detector and microwave power device etc. The characteristic excellent due to it and applying widely, is paid close attention to widely. Particularly gan (GaN) material in III-V race's semiconductor material, owing to it is in the commercial applications of semiconductor lighting stress, becomes the research focus in current global semiconductor field.
III group nitride material comprises AlN, GaN, InN and their alloy, by controlling its group part, can make the 6.2eV consecutive variations of the 0.9eV to AlN of its energy gap from InN, and corresponding wavelength region covers whole visible region, and may extend to ultraviolet region. This class material is direct band gap material, and there is thermal conductivity height, luminous efficiency height, specific inductivity is little, chemical property is stable, hardness is big and the feature such as high temperature resistant, is the ideal material making the devices such as laser diode (LD), high brightness blue green light LED (LED) and HFET (HFETs). Especially LED component wherein, obtains a wide range of applications in field of semiconductor illumination.
LED due to luminous efficiency height, low in energy consumption, containing toxic substance mercury, environmental protection, thus win concern. Along with the rapid improvement of the luminous efficiency of LED, the quick raising of brightness, LED has more and more wide market.
For GaN blue-ray LED, the monolithic sheet intrinsic parameter homogeneity of epitaxial wafer product is extremely important, and these parameters comprise wavelength, thickness, doping etc. In large-scale production process, due to sapphire (Al2O3) lattice mismatch between substrate and GaN material and thermal mismatching, epitaxial process can affect the overall warpage degree of LED, so that the warm field of epitaxial wafer and growth conditions can produce difference because of self warpage when grown quantum trap district (MQW), the wavelength of the LED grown out and electrical parameter monolithic sheet are interior by there is bigger difference, finally have influence on the monolithic homogeneity of LED product parameter.
Therefore, it is necessary to the epitaxial wafer warpage degree before a kind of LED growth technique of proposition, adjustment and change MQW growth, homogeneity in the monolithic sheet of optimization LED, it is to increase the monolithic sheet intrinsic parameter homogeneity of LED product, it is to increase product yield.
Chinese patent literature CN105070652A disclosed " GaN layer growth method and gained LED epitaxial film and LED chip ", it is on nucleating layer, grow two layers of GaN layer respectively, by regulating growth time, the pressure and temperature of these two layers of GaN layer, realize the segmentation to GaN crystal to grow, the GaN crystal making segmentation growth gained have a little difference cooperatively interacts, thus realize the lifting of the crystalline quality of GaN crystal, and reduce the lattice mismatch between GaN crystal and substrate crystal. The method just reduces lattice mismatch from the means of hypertrophy, and effect is general, is not study from the aspect directly changing growth warpage, does not realize the lifting to monolithic sheet intrinsic parameter homogeneity by changing warpage.
Chinese patent literature CN104409590A disclosed " LED epitaxial structure and growth method thereof " is that one grows Si in high temperature N-type GaN layer3N4/ GaN superlattice layer and the alternately arranged transition layer of the GaN layer do not adulterated, reduce the stress between high temperature N-type GaN layer and luminescent layer. Epitaxial wafer warpage degree before MQW can not effectively be regulated by the method, and inserts transition layer between high temperature N-type GaN and luminous zone, can affect the performance of LED product greatly.
Summary of the invention
The present invention is directed to the growth warpage issues that existing LED growing technology exists, it is provided that a kind of can improve LED parameter homogeneity, promote the LED epitaxial structure with warpage adjustment structure layer of the good rate of LED product and growth method thereof.
The LED epitaxial structure with warpage adjustment structure layer of the present invention, by the following technical solutions:
This epitaxial structure, comprise Sapphire Substrate, nucleating layer, roughened layer, high-temperature gan layer, high temperature N-type GaN layer, luminescent layer, P type AlGaN layer and P type GaN layer from bottom to top successively, being provided with warpage adjustment structure layer between high-temperature gan layer and high temperature N-type GaN layer, this warpage adjustment structure layer is Si3N4The superlattice layer of layer, the first GaN layer, AlGaN layer and the 2nd GaN layer, cycle life is 1-40.
The monocycle thickness of described warpage adjustment structure layer is 31-1930nm.
Described Si3N4The thickness of layer is 1-30nm.
The thickness of described first GaN layer is 10-800nm.
The thickness of described AlGaN layer is 10-300nm.
The thickness of described 2nd GaN layer is 10-800nm.
Above-mentioned epitaxial structure, utilizes Si3N4, lattice parameter difference between GaN, AlGaN and Sapphire Substrate and thermal expansion coefficient difference, by adjustment Si3N4The growth parameter(s) of layer and AlGaN layer, reaches the object regulating epitaxial wafer growth warpage degree, passes through Si simultaneously3N4/ GaN/AlGaN/GaN superlattice layer reduces the bottom growth extension of dislocation to luminescent layer, and induced dislocations is at Si3N4In/GaN/AlGaN/GaN superlattice layer, termination forms dislocation loop so that dislocation originally no longer continues to extend, it is to increase crystal growth quality.
The present invention has the growth method of the LED epitaxial structure of warpage adjustment structure layer, comprises the following steps:
(1) in the reaction chamber of metal-organic chemical vapor deposition equipment (MOCVD) equipment, on a sapphire substrate successively growing GaN nucleating layer, roughened layer, high-temperature gan layer;
This concrete growth conditions of three layers can adopt the growth conditions of existing conventional LED epitaxial structure.
(2) growing warpage adjustment structure layer, concrete steps are as follows:
1. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N into 20000-150000sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen), 3000-90000sccm3The SiH of (ammonia) and 5-200sccm4(silane), growth Si3N4Layer, thickness 1-30nm;
2. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm into 5-1000sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen) and 3000-90000sccm3(ammonia) or lead to the N of TEGa, 20000-150000sccm into 5-1000sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen) and 3000-90000sccm3(ammonia), grows the first GaN layer, thickness 10-800nm;
3. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm of TMAl, 5-1000sccm into 1-200sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen) and 3000-90000sccm3(ammonia), growth AlGaN layer, thickness 10-300nm;
4. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm into 5-1000sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen) and 3000-90000sccm3(ammonia) or lead to the N of TEGa, 20000-150000sccm into 5-1000sccm2The H of (nitrogen), 0-150000sccm2The NH of (hydrogen) and 3000-90000sccm3(ammonia), growth regulation two GaN layer, thickness 10-800nm;
1-40 cycle is grown by said process;
(3) on warpage adjustment structure layer, high temperature N-type GaN layer, luminescent layer, P type AlGaN layer and P type GaN layer is grown successively. This concrete growth conditions of four layers can adopt the growth conditions of existing conventional LED epitaxial structure.
Si in described warpage adjustment structure layer3N4Layer and AlGaN layer growth conditions can be the same or different, and work as Si3N4When layer is different with AlGaN layer growth conditions, change by the GaN layer transition condition of centre;
The present invention arranges warpage adjustment structure layer in LED epitaxial structure, before light-emitting layer grows, by regulating Si3N4Layer thickness and SiH4Flow, adjustment AlGaN layer thickness and Al component, coordinate, and regulates the warpage degree in epitaxial wafer process of growth. Improve in luminescent layer process of growth growth conditions homogeneity in extension blade, it is to increase LED product monolithic sheet intrinsic parameter homogeneity, it is to increase the good rate of LED.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention has the LED epitaxial structure of warpage adjustment structure layer.
Fig. 2 is the structural representation of warpage adjustment structure layer in the present invention.
In figure: 1, Sapphire Substrate; 2, nucleating layer; 3, roughened layer; 4, high-temperature gan layer; 5, warpage adjustment structure layer; 51, Si3N4Layer, the 52, first GaN layer, 53, AlGaN layer, the 54, the 2nd GaN layer, 6, high temperature N-type GaN layer; 7, luminescent layer; 8, P type AlGaN layer; 9, P type GaN layer.
Embodiment
As shown in Figure 1, the present invention has the LED epitaxial structure of warpage adjustment structure layer, comprise Sapphire Substrate 1, nucleating layer 2, roughened layer 3, high-temperature gan layer 4 from bottom to top successively, have warpage adjustment structure layer 5, high temperature N-type GaN layer 6, luminescent layer 7, P type AlGaN layer 8 and P type GaN layer 9, between high-temperature gan layer 4 and high temperature N-type GaN layer 6, be provided with warpage adjustment structure layer 5.As shown in Figure 2, warpage adjustment structure layer 5 is Si3N4The superlattice layer of layer the 51, first GaN layer 52, AlGaN layer 53 and the 2nd GaN layer 54, cycle life is 1-40, monocycle thickness 31-1930nm.
The growth temperature of warpage adjustment structure layer 5 is 700-1200 DEG C, and growth pressure is 50-300torr, wherein Si3N4Layer and AlGaN layer growth conditions can be the same or different, and work as Si3N4When layer is different with AlGaN layer growth conditions, changed by the GaN layer transition condition of centre; By regulating Si3N4Layer thickness and SiH4Flow, adjustment AlGaN layer thickness and Al component, coordinate, and regulates the warpage degree in epitaxial wafer process of growth.
The present invention has the growth method of the LED epitaxial structure of warpage adjustment structure layer, this epitaxial structure uses metal-organic chemical vapor deposition equipment (MOCVD) equipment to grow on a sapphire substrate with metal-organic chemical vapor deposition equipment method, specifically comprises the following steps:
(1) Sapphire Substrate is put into the reaction chamber of metal-organic chemical vapor deposition equipment (MOCVD) equipment, at 1000-1150 DEG C, under chamber pressure maintains the hydrogen atmosphere of 400-600torr, pyroprocessing Sapphire Substrate 1,3-10 minute time;
(2) temperature setting 500-560 DEG C, chamber pressure setting 400-600torr, in Sapphire Substrate 1, growth thickness is about the GaN nucleating layer 2 of 10-50nm;
(3) temperature setting 900-1100 DEG C, chamber pressure setting 400-600torr, growth roughened layer 3;
(4) temperature setting 950-1150 DEG C, chamber pressure setting 100-300torr, growth high-temperature gan layer 4, thickness 1-2 μm;
(5) grow warpage adjustment structure layer 5, comprise the following steps:
1. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the nitrogen (N into 20000-150000sccm2), the hydrogen (H of 0-150000sccm2), the ammonia (NH of 3000-90000sccm3) and the silane (SiH of 5-200sccm4), growth Si3N4Layer, thickness 1-30nm;
2. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the nitrogen (N of TMGa, 20000-150000sccm into 5-1000sccm2), the hydrogen (H of 0-150000sccm2) and the ammonia (NH of 3000-90000sccm3) or lead to the nitrogen (N of TEGa, 20000-150000sccm into 5-1000sccm2), the hydrogen (H of 0-150000sccm2) and the ammonia (NH of 3000-90000sccm3), grow the first GaN layer, thickness 10-800nm;
3. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the nitrogen (N of TMGa, 20000-150000sccm of TMAl, 5-1000sccm into 1-200sccm2), the hydrogen (H of 0-150000sccm2) and the ammonia (NH of 3000-90000sccm3), growth AlGaN layer, thickness 10-300nm;
4. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the nitrogen (N of TMGa, 20000-150000sccm into 5-1000sccm2), the hydrogen (H of 0-150000sccm2), the ammonia (NH of 3000-90000sccm3) or lead to the nitrogen (N of TEGa, 20000-150000sccm into 5-1000sccm2), the hydrogen (H of 0-150000sccm2) and the ammonia (NH of 3000-90000sccm3), growth regulation two GaN layer, thickness 10-800nm;
The warpage adjustment structure layer 5 in 1-40 cycle is grown by said process.
(6) temperature setting 1050-1100 DEG C, chamber pressure setting 100-300torr, growth high temperature N-type GaN layer 6, thickness 2-4 μm, Si doping content 5E+18-5E+19.
(7) temperature setting 650-850 DEG C, chamber pressure setting 100-300torr, the luminescent layer 7 of the InGaN/GaNMQW structure in 2-15 cycle of growth, thickness 100-180nm, Si doping content 1E+17-5E+17.
(8) temperature setting 900-990 DEG C, chamber pressure setting 80-350torr, the P type AlGaN layer 8, thickness 30-150nm, Al doping content 5E+19-5E20, Mg doping content 1E+19-9E+19 of magnesium is mixed in growth.
(9) temperature setting 850-990 DEG C, chamber pressure setting 100-300torr, the P type GaN layer 9, thickness 30-150nm, Mg doping content 1E+19-2E+20 of magnesium is mixed in growth.
(10) temperature setting 600-750 DEG C, is incubated 3-10 minute under nitrogen atmosphere, is cooled to room temperature.
Claims (7)
1. one kind has the LED epitaxial structure of warpage adjustment structure layer, comprise Sapphire Substrate, nucleating layer, roughened layer, high-temperature gan layer, high temperature N-type GaN layer, luminescent layer, P type AlGaN layer and P type GaN layer from bottom to top successively, it is characterized in that: be provided with warpage adjustment structure layer between high-temperature gan layer and high temperature N-type GaN layer, this warpage adjustment structure layer is Si3N4The superlattice layer of layer, the first GaN layer, AlGaN layer and the 2nd GaN layer, cycle life is 1-40.
2. the LED epitaxial structure with warpage adjustment structure layer according to claim 1, is characterized in that: the monocycle thickness of described warpage adjustment structure layer is 31-1930nm.
3. the LED epitaxial structure with warpage adjustment structure layer according to claim 1, is characterized in that: described Si3N4The thickness of layer is 1-30nm.
4. the LED epitaxial structure with warpage adjustment structure layer according to claim 1, is characterized in that: the thickness of described first GaN layer is 10-800nm.
5. the LED epitaxial structure with warpage adjustment structure layer according to claim 1, is characterized in that: the thickness of described AlGaN layer is 10-300nm.
6. the LED epitaxial structure with warpage adjustment structure layer according to claim 1, is characterized in that: the thickness of described 2nd GaN layer is 10-800nm.
7. a growth method described in claim 1 with the LED epitaxial structure of warpage adjustment structure layer, is characterized in that, comprise the following steps:
(1) in the reaction chamber of metal-organic chemical vapor deposition equipment, on a sapphire substrate successively growing GaN nucleating layer, roughened layer, high-temperature gan layer;
(2) growing warpage adjustment structure layer, concrete steps are as follows:
1. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N into 20000-150000sccm2, 0-150000sccm H2, 3000-90000sccm NH3With the SiH of 5-200sccm4, growth Si3N4Layer, thickness 1-30nm;
2. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm into 5-1000sccm2, 0-150000sccm H2With the NH of 3000-90000sccm3Or lead to the N of TEGa, 20000-150000sccm into 5-1000sccm2, 0-150000sccm H2With the NH of 3000-90000sccm3, grow the first GaN layer, thickness 10-800nm;
3. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm of TMAl, 5-1000sccm into 1-200sccm2, 0-150000sccm H2With the NH of 3000-90000sccm3, growth AlGaN layer, thickness 10-300nm;
4. temperature setting 700-1200 DEG C, chamber pressure setting 50-300torr, leads to the N of TMGa, 20000-150000sccm into 5-1000sccm2, 0-150000sccm H2With the NH of 3000-90000sccm3Or lead to the N of TEGa, 20000-150000sccm into 5-1000sccm2, 0-150000sccm H2With the NH of 3000-90000sccm3, growth regulation two GaN layer, thickness 10-800nm;
1-40 cycle is grown by said process;
(3) on warpage adjustment structure layer, high temperature N-type GaN layer, luminescent layer, P type AlGaN layer and P type GaN layer is grown successively.
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