CN102031560A - Method for preparing large-size GaN self-support substrate - Google Patents
Method for preparing large-size GaN self-support substrate Download PDFInfo
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- CN102031560A CN102031560A CN2009102353365A CN200910235336A CN102031560A CN 102031560 A CN102031560 A CN 102031560A CN 2009102353365 A CN2009102353365 A CN 2009102353365A CN 200910235336 A CN200910235336 A CN 200910235336A CN 102031560 A CN102031560 A CN 102031560A
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Abstract
The invention relates to a method for preparing a large-size GaN self-support substrate, which comprises the following steps of: 1. firstly, growing a layer of ZnO membrane on a substrate; 2. growing a low-temperature buffer layer on the ZnO membrane to form a sample; 3. growing a GaN thick membrane on the low-temperature buffer layer at high temperature in a hydride vapour phase epitaxy system; and 4. after growing in the hydride vapour phase epitaxy system at high temperature, directly separating the GaN thick membrane from the substrate to form a large-size GaN self-support substrate because corrosive gases, such as HCL, NH3, and the like in the hydride vapour phase epitaxy system corrodes the ZnO membrane.
Description
Technical field
The present invention relates to utilize methods such as hydride gas-phase epitaxy to prepare the method for large size GaN self-supporting substrate.
Background technology
With GaN and alloy thereof is that the third generation semiconductor material of representative is the novel semiconductor material of extremely paying attention in the world in recent ten years, many excellent properties such as it has that energy gap is big, electronics saturation drift velocity height, specific inductivity are little, good heat conductivity, Stability Analysis of Structures all have great application prospect at photoelectron and microelectronics technology.In the optoelectronic areas,, covered the wave band from ruddiness to the ultraviolet, can make green, blueness and even ultraviolet band luminescent device and white-light illuminating because the energy gap of III group-III nitride is adjustable continuously in the 0.7-6.2eV scope.In addition, the ultraviolet leds that rises has also shown special purposes in silk screen printing, polymer cure, environment protection recently, has excited researchist's research interest greatly.The GaN laser apparatus also fully develops talents at area information storage, also can be applicable to medical diagnosis, seabed and visits and dive and all respects such as communication.
The preparation of GaN body monocrystalline is difficulty relatively, is difficult to obtain large size and mass ratio body monocrystalline GaN substrate preferably, so the epitaxy of GaN is normally carried out in the mode of hetero epitaxy.But theoretical and experiment shows that all when adopting GaN to make substrate iso-epitaxy device, device performance is greatly improved.Therefore make self-supporting GaN substrate and become the focus that people pay close attention to.
Present large-area GaN self-supporting substrate all is by vapor phase growth GaN thick film on foreign substrate usually, obtains after then former foreign substrate being separated.Wherein Sapphire Substrate is the most frequently used substrate.In order to obtain the self-supporting substrate, Sapphire Substrate must be removed.The sapphire quality is hard, and chemical property is stable, therefore is difficult to remove by the method for chemical corrosion or mechanical grinding.The method of normal at present use laser lift-off is separated GaN with Sapphire Substrate.But laser lift-off technique cost costliness; And in the process of laser lift-off, the high pressure gas that produce behind the GaN pyrolytic decomposition cause damage to the GaN self-supporting substrate of preparation easily at the interface, thereby it is light then on GaN self-supporting substrate, produce the quality of device after a large amount of dislocations and the tiny crack influence, thereby heavy then make the complete cracked yield rate that reduces greatly of GaN self-supporting substrate.
Summary of the invention
The present invention seeks to: the technology that adopts ZnO film and hydride gas-phase epitaxy system to combine, by peeling off preparation high quality, large-sized GaN self-supporting substrate certainly.
Solution of the present invention is:
The invention provides a kind of method for preparing large size GaN self-supporting substrate, comprise following steps:
Step 1: the layer of ZnO film of at first on substrate, growing;
Step 2: low temperature growth buffer layer on ZnO film forms sample;
Step 3: in the hydride gas-phase epitaxy system, high growth temperature GaN thick film on low temperature buffer layer;
Step 4: in the hydride gas-phase epitaxy system behind the high growth temperature, because of HCl in the hydride gas-phase epitaxy system and NH
3Deng corrosive gases,, the GaN thick film is directly separated from substrate form large-sized GaN self-supporting substrate ZnO film 2 corrosion.
The material of the wherein said substrate that is used for extension self-supporting GaN thick film is: sapphire, spinel, GaN, AlN, GaAs, Si, SiC, LiAlO
2, LiGaO
2, ZrB
2Or HfB
2In a kind of.
The wherein growth of ZnO film is the method that adopts the source metal vapour phase epitaxy, and the source material that adopts in this method is metallic zinc and deionized water, and the reaction equation of metallic zinc and deionized water is:
The ZnO film of wherein growing except adopting the method for source metal vapour phase epitaxy, can also adopt the method for metal organic chemical vapor deposition, molecular beam epitaxy, atomic layer epitaxy, sputter, pulsed laser deposition, spray pyrolysis or sol-gel.
Wherein ZnO film is the ZnO film of monocrystal thin films or polycrystalline or amorphous, and the growth thickness of this ZnO film is 0.3-50 μ m.
The material of wherein said low temperature buffer layer is GaN, InGaN, AlGaN, InAlGaN or AlN.
Wherein the growth temperature of low temperature buffer layer is at 400-800 ℃, and low temperature buffer layer is to adopt the method for rheotaxy, metal organic chemical vapor deposition, the transmission of enclosed space gas phase or hydride gas-phase epitaxy to prepare.
Wherein the thickness of low temperature buffer layer is 0.3-100 μ m, and low temperature buffer layer has covered the surface of ZnO film fully.
Wherein the growth temperature of GaN thick film is 900-1150 ℃, and growth time is greater than 30min, and growth thickness is 0.05-50mm.
Technical characterstic of the present invention is:
1, use ZnO film as sacrifice layer, ZnO film also can play the effect of nucleating layer in as oneself sacrifice layer of peeling off.
2, adopt rheotaxy, metal organic chemical vapor deposition, enclosed space gas phase to transmit on ZnO film or the mode of hydride gas-phase epitaxy one deck low temperature buffer layer of growing, the temperature of the growth of buffer layer should be lower than 800 ℃, thereby avoids ZnO film to be destroyed.
3, high growth temperature high quality GaN thick film in the hydride gas-phase epitaxy system at last, corrosive gasess such as HCl that exists in the hydride gas-phase epitaxy system or NH3 can corrode ZnO film from the side, but can not be from the front etch ZnO film, the last layer low temperature buffer layer because grown in the front.The material of buffer layer is more than the material settling out of ZnO film, so can not be corroded.
4, after the process of growth of hydride gas-phase epitaxy is finished, because ZnO film is corroded, so the GaN thick film has formed the self-supporting substrate from stripping down from substrate.And substrate can be reused after cleaning.
Description of drawings
For further specifying concrete technology contents of the present invention, below in conjunction with embodiment and accompanying drawing describes in detail as after, wherein:
Fig. 1 is the diagrammatic cross-section that one embodiment of the invention is made flow process;
Fig. 2 is in the hydride gas-phase epitaxy system during high growth temperature GaN thick film, corrosive gases corrosion ZnO film, thus obtain the synoptic diagram of self-supporting GaN substrate;
Fig. 3 be in the example 1 as (0002) of the ZnO film of sacrifice layer and nucleating layer to the X-ray diffraction rocking curve.
Embodiment
Embodiment one
See also Fig. 1, shown in Figure 2, a kind of method for preparing large size GaN self-supporting substrate comprises following steps:
Step 1: the layer of ZnO film 2 of at first on substrate 1, growing; The material of the wherein said substrate 1 that is used for extension self-supporting GaN thick film 4 is: sapphire, spinel, GaN, AlN, GaAs, Si, SiC, LiAlO
2, LiGaO
2, ZrB
2Or HfB
2In a kind of, this example selects for use sapphire as substrate; The method of source metal vapour phase epitaxy is adopted in the wherein growth of ZnO film 2 in this example, and the source material that adopts in this method is metallic zinc and deionized water, and the reaction equation of metallic zinc and deionized water is:
This reaction is a reversible reaction.By continuous eliminating tail gas and adjust source material and the flow of carrier gas, control reaction and reach running balance, make Metal Zn and H
2O reacts endlessly, the advantage of this method is that growth temperature is low, growth velocity is fast, method is simple, cost is low, help forming industrialization technology, but this method growth thickness is at the ZnO film of 0.3-50 μ m, the thick ZnO film 2 of growth 1 μ m in this example, and resulting ZnO film is a single crystal film, sees also shown in Figure 3ly, and (0002) of ZnO film 2 is 190 second of arcs to the halfwidth of X-ray diffraction rocking curve; The ZnO film 2 of wherein growing except adopting the source metal vapour phase epitaxy, also can adopt the method growth of metal organic vapor, molecular beam epitaxy, atomic layer epitaxy, sputter, pulsed laser deposition, spray pyrolysis or sol-gel; The ZnO film 2 of the method preparation by the source metal vapour phase epitaxy in this example is a monocrystal thin films, and except the ZnO film of monocrystalline, the ZnO film of polycrystalline or amorphous also can be used; The growth thickness of this ZnO film 2 is 0.3-50 μ m.
Step 2: low temperature growth buffer layer 3 on ZnO film 2, the material of wherein said low temperature buffer layer 3 are GaN, InGaN, AlGaN, InAlGaN or AlN, and this example adopts low temperature GaN material preparation low temperature buffer layer 3; Wherein the growth temperature of low temperature buffer layer 3 is at 400-800 ℃, low temperature buffer layer 3 is to adopt the method for rheotaxy, metal organic vapor, the transmission of enclosed space gas phase or hydride gas-phase epitaxy to prepare, this example has the Sapphire Substrate of ZnO film 2 to place hydride gas-phase epitaxy equipment to carry out the growth of GaN low temperature buffer layer 3 growth, destroyed in order to prevent ZnO film, the growth temperature of GaN low temperature buffer layer 3 is 650 ℃, and low-temperature epitaxy continues 30 minutes altogether; Wherein the thickness of low temperature buffer layer 3 is 0.3-100 μ m, and the thickness of the GaN low temperature buffer layer 3 that the method by hydride gas-phase epitaxy in this example prepares is about 0.5 μ m, and low temperature buffer layer 3 has covered the surface of ZnO film 2 fully.
Step 3: high growth temperature GaN thick film 4 in the hydride gas-phase epitaxy system; Wherein the growth temperature of GaN thick film 4 is 900-1150 ℃, and growth time is greater than 30min, and growth thickness is 0.05-50mm; Low temperature buffer layer 3 and GaN thick film 4 all are to finish in same hydride gas-phase epitaxy system in this example, so can reduce cost, reduce pollution in process of growth; After low-temperature epitaxy is finished the intrasystem temperature of hydride gas-phase epitaxy is elevated to 1050 ℃, thereby the high growth temperature that carries out 1.5 hours prepares the GaN thick film 4 of 150 μ m, hydride gas-phase epitaxy intrasystem high temperature corrosion gas HCl and NH3 etc. can not be from front etch ZnO films 2 during high growth temperature, because the positive low temperature buffer layer that many of last layer material of having grown than the material settling out of ZnO film, so can not be corroded, but can corrode ZnO film 2 from the side by the direction of Fig. 2 arrow indication.
Step 4: in the hydride gas-phase epitaxy system behind the high growth temperature, because of HCl in the hydride gas-phase epitaxy system and NH
3Deng corrosive gases, with ZnO film 2 corrosion, GaN thick film 4 is directly separated from substrate 1 form large-sized GaN self-supporting substrate, and HCl in the hydride gas-phase epitaxy system and NH
3Can not corrode GaN etc. the High Temperature Gas body, thus to the quality of the large size GaN self-supporting substrate that finally obtains without any influence; And Sapphire Substrate 1 can also reuse after cleaning.
Embodiment two
Please consult Fig. 1, shown in Figure 2 again, present embodiment 2 is substantially the same manner as Example 1, and its difference is:
(1) method that adopts spray pyrolysis for preparing of ZnO film 2 prepares in the step 1, and the ZnO film 2 of preparation is a polycrystal film, and its thickness is 0.5 μ m.The advantage of spray pyrolysis method is that growth temperature is low, and method is simple, and cost is very low.
(2) adopt the method for metal organic chemical vapor deposition under 600 ℃ condition, to grow the InGaN film of 500nm in the step 2 as low temperature buffer layer; InGaN low temperature buffer layer 3 helps to reduce the defect concentration of GaN thick film 4, improves the crystal mass of the large size GaN self-supporting substrate that finally obtains.
(3) hydride gas-phase epitaxy intrasystem high temperature corrosion gas HCl and NH during high growth temperature
3Direction by Fig. 2 arrow indication is corroded ZnO film 2 from the side, because ZnO film 2 is a polycrystal film in this example, so easier intrasystem high temperature corrosion gaseous corrosion of thing vapour phase epitaxy that is hydrogenated, strip down from Sapphire Substrate 1 so GaN thick film 4 is easier, therefore can improve the yield rate of preparation large size GaN self-supporting substrate.
Although at length show and described the present invention with reference to its certain embodiments, should also be noted that technician for this professional domain, can carry out various changes to its form and details, and not break away from the scope of the present invention that claims limit.
Claims (9)
1. method for preparing large size GaN self-supporting substrate comprises following steps:
Step 1: the layer of ZnO film of at first on substrate, growing;
Step 2: low temperature growth buffer layer on ZnO film forms sample;
Step 3: in the hydride gas-phase epitaxy system, high growth temperature GaN thick film on low temperature buffer layer;
Step 4: in the hydride gas-phase epitaxy system, behind the high growth temperature,,, the GaN thick film is directly separated from substrate form large-sized GaN self-supporting substrate with ZnO film 2 corrosion because of corrosive gasess such as HCl in the hydride gas-phase epitaxy system and NH3.
2. the method for preparing large size GaN self-supporting substrate according to claim 1, the material of the wherein said substrate that is used for extension self-supporting GaN thick film is: sapphire, spinel, GaN, AlN, GaAs, Si, SiC, LiAlO
2, LiGaO
2, ZrB
2Or HfB
2In a kind of.
3. the method for preparing large size GaN self-supporting substrate according to claim 1, the wherein growth of ZnO film, be the method that adopts the source metal vapour phase epitaxy, the source material that adopts in this method is metallic zinc and deionized water, and the reaction equation of metallic zinc and deionized water is:
4. the method for preparing large size GaN self-supporting substrate according to claim 1, the ZnO film of wherein growing, except adopting the method for source metal vapour phase epitaxy, can also adopt the method for metal organic chemical vapor deposition, molecular beam epitaxy, atomic layer epitaxy, sputter, pulsed laser deposition, spray pyrolysis or sol-gel.
5. according to claim 1, the 3 or 4 described methods that prepare large size GaN self-supporting substrate, wherein ZnO film is the ZnO film of monocrystal thin films or polycrystalline or amorphous, and the growth thickness of this ZnO film is 0.3-50 μ m.
6. the method for preparing large size GaN self-supporting substrate according to claim 1, the material of wherein said low temperature buffer layer is GaN, InGaN, AlGaN, InAlGaN or AlN.
7. according to claim 1 or the 6 described methods that prepare large size GaN self-supporting substrate, wherein the growth temperature of low temperature buffer layer is at 400-800 ℃, and low temperature buffer layer is to adopt the method for rheotaxy, metal organic chemical vapor deposition, the transmission of enclosed space gas phase or hydride gas-phase epitaxy to prepare.
8. according to claim 1 or the 7 described methods that prepare large size GaN self-supporting substrate, wherein the thickness of low temperature buffer layer is 0.3-100 μ m, and low temperature buffer layer has covered the surface of ZnO film fully.
9. the method for preparing large size GaN self-supporting substrate according to claim 1, wherein the growth temperature of GaN thick film is 900-1150 ℃, and growth time is greater than 30min, and growth thickness is 0.05-50mm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956417A (en) * | 2014-05-08 | 2014-07-30 | 中国科学院半导体研究所 | Method for preparing non-polar surface or semi-polar surface single crystal semiconductor self-supporting substrate |
| CN104178807A (en) * | 2014-08-06 | 2014-12-03 | 上海世山科技有限公司 | Method for obtaining self-supporting gallium nitride substrates by using thermal decomposition characteristics |
| CN105986321A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for growing GaAs epitaxial film on Ge substrate |
| CN110767533A (en) * | 2019-10-24 | 2020-02-07 | 华南理工大学 | Wafer-level MoS2Method for preparing single-layer film |
| CN107978659B (en) * | 2016-10-21 | 2021-05-28 | 三星电子株式会社 | Method for manufacturing gallium nitride substrate |
| CN115233304A (en) * | 2022-06-17 | 2022-10-25 | 西安电子科技大学 | Preparation method of self-supporting GaN film based on AlPN buffer layer |
-
2009
- 2009-09-30 CN CN2009102353365A patent/CN102031560A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956417A (en) * | 2014-05-08 | 2014-07-30 | 中国科学院半导体研究所 | Method for preparing non-polar surface or semi-polar surface single crystal semiconductor self-supporting substrate |
| CN104178807A (en) * | 2014-08-06 | 2014-12-03 | 上海世山科技有限公司 | Method for obtaining self-supporting gallium nitride substrates by using thermal decomposition characteristics |
| CN105986321A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for growing GaAs epitaxial film on Ge substrate |
| CN105986321B (en) * | 2015-02-16 | 2018-08-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | In the method for Ge Grown GaAs epitaxial films |
| CN107978659B (en) * | 2016-10-21 | 2021-05-28 | 三星电子株式会社 | Method for manufacturing gallium nitride substrate |
| CN110767533A (en) * | 2019-10-24 | 2020-02-07 | 华南理工大学 | Wafer-level MoS2Method for preparing single-layer film |
| CN110767533B (en) * | 2019-10-24 | 2022-05-24 | 华南理工大学 | Wafer-level MoS2Method for preparing single-layer film |
| CN115233304A (en) * | 2022-06-17 | 2022-10-25 | 西安电子科技大学 | Preparation method of self-supporting GaN film based on AlPN buffer layer |
| CN115233304B (en) * | 2022-06-17 | 2023-12-22 | 西安电子科技大学 | Preparation method of self-supporting GaN film based on AlPN buffer layer |
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Application publication date: 20110427 |