CN111463325B - Preparation method of large-size GaN thick film - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 22
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 11
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 18
- 229910052594 sapphire Inorganic materials 0.000 description 9
- 239000010980 sapphire Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 6
- 238000000407 epitaxy Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001657 homoepitaxy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a large-size GaN thick film, which comprises the steps of firstly, adopting an MOCVD epitaxial technology on a substrate, and epitaxially growing a GaN template layer through a buffer layer by utilizing a TMG source; then switching the TMG source coarse body on the GaN template layer by adopting the MOCVD epitaxial technology to grow a GaN stress release layer; growing a GaN thick film layer on the GaN template layer with the GaN stress release layer by adopting an HVPE method; and finally, stripping the substrate to obtain the large-size GaN thick film. According to the invention, the TMG source coarse body is switched through the MOCVD process, and the GaN epitaxial layer with higher dislocation density and poorer crystal quality is epitaxially grown to release stress through the impurity doping of the TMG source coarse body, so that stress release is provided for the subsequent thick-film GaN growth, the growth cracks of the large-size GaN layer are reduced, and the quality of the large-size GaN thick film is improved.
Description
Technical Field
The invention relates to a preparation method of a large-size GaN thick film, belonging to the technical field of semiconductor photoelectric material preparation.
Background
At present, the wide-band-gap GaN single crystal material can be applied to the preparation of high-frequency, high-power and high-temperature resistant microelectronic devices, realizes optoelectronic devices with the luminous wavelength covering the whole visible light wave band, and has great application prospects in the aerospace military field and the commercial fields of daily illumination, display and the like.
At present, the mature HVPE and MOCVD epitaxy for preparing GaN materials are epitaxial technologies grown on a heterogeneous substrate, and crystal materials grown epitaxially are high in dislocation density and large in stress due to mismatch of crystal lattices and thermal expansion between the substrate and the epitaxial layer, so that the phenomena of warping, cracking and the like are easy to occur, the working efficiency and the service life of a device are influenced, and the application of the device in the field of semiconductor electronics is restricted; the homoepitaxy of the GaN single crystal substrate material can greatly improve the crystal quality of an epitaxial film, reduce the dislocation density, and improve the working life and the luminous efficiency of a device, so that the high-quality GaN single crystal material is urgently needed, and a GaN substrate is stripped to realize the homoepitaxy technology.
However, the preparation of GaN single crystal materials is very difficult, and the growth difficulty of GaN epitaxial materials is very large due to the lack of a substrate matched with the GaN single crystal materials; in addition, as the market for semiconductor lighting and displays develops, the demand for substrates is increasingly turning to larger dimensions, which presents greater difficulties and challenges to GaN material growth.
At present, the GaN substrate materials at home and abroad are generally separately processed by MOCVD and HVPE epitaxy, namely, a GaN template layer is grown on a substrate such as sapphire by MOCVD, a thick film GaN is grown on the GaN template layer by HVPE, and finally the substrate such as sapphire is stripped; high-quality GaN materials have been greatly developed, but compared with other semiconductor materials, a GaN thick film grown on a substrate of sapphire and the like still has high defect density, the dislocations are represented as non-radiative recombination centers when the device works to influence the efficiency of the device, the increase of leakage current is caused to lead the device to be rapidly aged, and meanwhile, warping cracks caused by residual stress in the GaN thick film on a heterogeneous substrate of large-size sapphire and the like are difficult to overcome by a GaN heteroepitaxy technology.
The high-purity metal organic compound MO source is a key material and a dopant of an epitaxial growth semiconductor compound, the higher the purity of the MO source is, the fewer impurities are, the higher the product quality is, the requirement of the epitaxial growth of the semiconductor material in the photoelectric industry on the purity of impurity elements is generally more than 6N (the purity is 99.9999%), the purification methods such as recrystallization, sublimation, rectification and the like are commonly used for purification, complex components, an inert additive extrusion method, an adsorption method, an adduct purification method and the like are successively developed at home and abroad for obtaining the high-purity MO source, however, the purification process is easy to introduce the impurity elements, has high requirement on the tightness of equipment, poor safety, potential safety hazard and the like, and the preparation cost of the MO; the most important point for evaluating the quality of the MO source is to see whether the photoelectric performance of a product obtained by using the MO source epitaxy meets the performance requirements of a device and the cost.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a large-size GaN thick film.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the large-size GaN thick film comprises the steps of switching a TMG source on a GaN template layer epitaxially grown by MOCVD to grow a GaN stress release layer in a rough body mode, and then growing a GaN thick film layer on the GaN template layer with the GaN stress release layer by adopting an HVPE method; and finally, stripping the substrate to obtain a large-size GaN thick film, wherein the method comprises the following steps:
1) carrying out epitaxial growth on a GaN template layer on the substrate by adopting an MOCVD epitaxial technology and utilizing a TMG source through a buffer layer;
2) switching the TMG source coarse body on the GaN template layer by adopting an MOCVD epitaxial technology to grow a GaN stress release layer;
3) growing a GaN thick film layer on the GaN template layer with the GaN stress release layer by adopting an HVPE method;
4) and stripping the substrate to obtain the large-size GaN thick film.
Further, the preparation method of the large-size GaN thick film comprises the following steps of 1), providing a substrate; growing a low-temperature GaN buffer layer of 20-60 nm on the substrate, wherein the growth temperature is 550-650 ℃; and growing a GaN template layer with the thickness of 0.1-10 mu m on the low-temperature GaN buffer layer, wherein the growth temperature is 1200-1250 ℃.
Further, in the preparation method of the large-size GaN thick film, in the step 2), after the growth of the GaN template layer is finished, the TMG source is closed, the TMG source coarse body is opened, and the GaN stress release layer is grown at the growth temperature of 950-1250 ℃.
Further, in the preparation method of the large-size GaN thick film, the purity of the TMG source is not lower than 99.9999%, the concentration of the impurity element is less than 1ppm, the crude purity of the TMG source is 99.99% -99.999%, and the concentration of the impurity element is 10-100 ppm.
Further, in the above method for preparing a large-size GaN thick film, the TMG source refers to an electronic-grade TMG source that has undergone a high purification process during synthesis and purification, and the bold TMG source refers to a TMG source that has not undergone a high purification process during synthesis and purification.
Further, in the preparation method of the large-size GaN thick film, in the step 2), the thickness of the GaN stress release layer is 0.01-1 μm.
Further, the preparation method of the large-size GaN thick film comprises the following steps of 3), placing a composite structure formed by the GaN stress release layer, the GaN template layer, the GaN buffer layer and the substrate in an HVPE system; controlling the temperature of the growth area to be 950-1100 ℃, the pressure in the cavity to be 250-650 mbar, the total carrier gas flow to be 2000-6000 ml, controlling the inflow V/II value of the source to be 10-100, and growing the GaN thick film layer.
Further, in the preparation method of the large-size GaN thick film, in the step 3), the thickness of the GaN thick film layer is 100-1000 μm.
Further, in the above method for preparing the large-size GaN thick film, in step 4), the buffer layer and the substrate are removed by a laser lift-off method or a chemical etching lift-off method.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and is embodied in the following aspects:
the method comprises the following steps of switching a TMG source coarse body through an MOCVD process, and carrying out epitaxial growth on a GaN epitaxial layer with higher dislocation density and poorer crystal quality to release stress through higher impurity doping of the TMG source coarse body, thereby providing stress release for subsequent thick-film GaN growth, reducing growth cracks of a large-size GaN layer and improving the quality of the large-size GaN thick film;
the TMG source coarse body is switched through the MOCVD process to prepare the GaN stress release layer, and compared with the MOCVD epitaxial process, the growth of stress is adjusted and controlled, the process is simple, and the controllability is strong;
and thirdly, the TMG source coarse body is switched through the MOCVD process, so that the use consumption of the high-purity TMG source can be reduced, and the growth cost of the GaN epitaxial material can be reduced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1: the process flow of the invention is schematic;
FIG. 2: the invention is a schematic view of a layered structure.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures. Meanwhile, in the description of the present invention, the directional terms and the sequence terms, etc. are used only for distinguishing the description, and are not to be construed as indicating or implying relative importance.
Example 1
Growing a layer of low-temperature GaN buffer layer with the thickness of 20nm on a sapphire substrate by adopting the MOCVD technology, wherein the Ga source required for growth is high-purity TMG, and the growth atmosphere is H2The atmosphere, the growth temperature is 600 ℃, and the growth pressure is 650 mbar;
growing a GaN template layer 21 with the thickness of 2 μm on the low-temperature GaN buffer layer, wherein the Ga source required for growth is high-purity TMG, and the growth atmosphere is H2The atmosphere, the growth temperature is 1205 ℃, and the growth pressure is 300 mbar;
continuing to adopt MOCVD epitaxy technology on the GaN template layer 21, closing the TMG source, opening the TMG source coarse body, and growing a GaN stress release layer 22 with the thickness of 0.01 μm;
placing a composite structure formed by the GaN stress release layer 22, the GaN template layer 21, the GaN buffer layer and the substrate in an HVPE system;
controlling the temperature of the growth region to 1050 ℃, the pressure in the cavity to 500mbar, and adopting N2The carrier gas is the total carrier gas flow rate 4000, the source inflow V/II value is controlled to be 50, and the GaN thickness layer 23 grows to be 100 mu m in thickness;
and removing the buffer layer and the sapphire substrate by adopting a laser stripping method to prepare the GaN thick film structure 2.
Example 2
Example 2 differs from example 1 in that the thickness of the GaN stress relaxation layer 22 was grown to 0.5 μm, and the thickness of the HVPE grown GaN thickness layer 23 was 350 μm;
and removing the buffer layer and the sapphire substrate by adopting a laser stripping method to prepare the GaN thick film structure 2.
Example 3
Example 2 differs from example 1 in that the thickness of the GaN stress relaxation layer 22 was grown to 1 μm, and the thickness of the HVPE grown GaN thickness layer 23 was 800 μm;
and removing the buffer layer and the sapphire substrate by adopting a laser stripping method to prepare the GaN thick film structure 2.
Example 4
Example 4 is different from example 1 in that the growth pressure for growing the GaN stress relief layer 22 is adjusted to 450mbar, and the thickness of the HVPE grown GaN thick film layer 23 is 350 μm;
and removing the buffer layer and the sapphire substrate by adopting a laser stripping method to prepare the GaN thick film structure 2.
In examples 1, 2, 3 and 4, the GaN thick films 23 with different thicknesses and low dislocation densities can be prepared by adjusting the thickness or pressure of the GaN stress release layer 22, and the dislocation density is controlled at 5 × 107cm-2、6×106cm-2、8×105cm-2And 3X 106cm-2The process is simple and easy to control.
The larger the thickness of the GaN stress release layer 22 is, the more remarkable the effect of releasing the GaN stress of the thick film grown by subsequent HVPE is, and the thickness of the GaN stress release layer 22 can be adjusted to match the thickness of the GaN thick film layer 23 according to the process.
In conclusion, the invention switches the coarse TMG (trimethyl gallium) source through the MOCVD process, prepares the GaN epitaxial layer with higher dislocation density and poorer crystal quality through the impurity doping of the TMG source coarse body, provides stress release for the subsequent thick film GaN growth, reduces the growth cracks of the large-size GaN layer, and improves the quality of the large-size GaN thick film;
the TMG source coarse body is switched through the MOCVD process, and compared with the MOCVD epitaxial process, the growth of the stress is adjusted and controlled, the process is simple, and the controllability is strong;
the crude body of the simple TMG source is switched by the MOCVD process, so that the use consumption of the TMG source is reduced, and the growth cost of the GaN epitaxial material is reduced.
The method has the advantages of simple process and strong controllability, can prepare the GaN thick films with different thicknesses by adjusting the thickness of the stress release layer, simultaneously reduces the consumption of the high-purity TMG source, and reduces the growth cost of the GaN epitaxial material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and shall be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Claims (9)
1. The preparation method of the large-size GaN thick film is characterized by comprising the following steps: switching a TMG source on a GaN template layer epitaxially grown by MOCVD to grow a GaN stress release layer in a rough body, and then growing a GaN thick film layer on the GaN template layer with the GaN stress release layer by adopting an HVPE method; and finally, stripping the substrate to obtain a large-size GaN thick film, wherein the method comprises the following steps:
1) a GaN template layer (21) is epitaxially grown on the substrate through the buffer layer by adopting an MOCVD epitaxial technology and utilizing a TMG source;
2) switching TMG source coarse bodies and growing a GaN stress release layer (22) on the GaN template layer (21) by adopting an MOCVD epitaxial technology;
3) growing a GaN thick film layer (23) on the GaN template layer (21) with the GaN stress release layer (22) by adopting an HVPE method;
4) and stripping the substrate to obtain the large-size GaN thick film.
2. The method of claim 1, wherein: step 1), providing a substrate; growing a low-temperature GaN buffer layer of 20-60 nm on the substrate, wherein the growth temperature is 550-650 ℃; and growing a GaN template layer (21) with the thickness of 0.1-10 mu m on the low-temperature GaN buffer layer, wherein the growth temperature is 1200-1250 ℃.
3. The method of claim 1, wherein: and 2), closing a TMG source after the growth of the GaN template layer (21) is finished, opening the TMG source coarse body, and growing a GaN stress release layer (22) at the growth temperature of 950-1250 ℃.
4. The method of preparing a large-sized GaN thick film according to claim 1 or 3, wherein: the purity of the TMG source is not lower than 99.9999%, the concentration of impurity elements is less than 1ppm, the crude purity of the TMG source is 99.99-99.999%, and the concentration of the impurity elements is 10-100 ppm.
5. The method of preparing a large-sized GaN thick film according to claim 1 or 3, wherein: the TMG source refers to an electronic grade TMG source which is subjected to a high-purification process in the synthetic purification process, and the crude TMG source refers to the TMG source which is not subjected to the high-purification process in the synthetic purification process.
6. The method of claim 1, wherein: and step 2), the thickness of the GaN stress release layer (22) is 0.01-1 mu m.
7. The method of claim 1, wherein: step 3), placing a composite structure formed by the GaN stress release layer (22), the GaN template layer (21), the GaN buffer layer and the substrate in an HVPE system; controlling the temperature of the growth area to be 950-1100 ℃, the pressure in the cavity to be 250-650 mbar, the total carrier gas flow to be 2000-6000 ml, controlling the source inflow V/II value to be 10-100, and growing the GaN thick film layer (23).
8. The method of claim 1, wherein: and step 3), the thickness of the GaN thick film layer (23) is 100-1000 mu m.
9. The method of claim 1, wherein: and 4) removing the buffer layer and the substrate by adopting a laser stripping method or a chemical corrosion stripping method.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431017A (en) * | 2008-12-03 | 2009-05-13 | 南京大学 | Method for improving GaN thick film integrality on sapphire substrate |
| CN101519799A (en) * | 2008-02-27 | 2009-09-02 | 中国科学院半导体研究所 | Method for preparing non-polar GaN thick film on sapphire substrate |
| CN101685768A (en) * | 2008-09-23 | 2010-03-31 | 北京大学 | Method for preparing self-supporting mono-crystal gallium nitride substrate |
| CN102201332A (en) * | 2011-05-08 | 2011-09-28 | 北京燕园中镓半导体工程研发中心有限公司 | Preparation method of GaN substrate |
| CN103647008A (en) * | 2013-12-31 | 2014-03-19 | 中国科学院半导体研究所 | Method for growing semi-polarity GaN (gallium nitride) thick film |
| CN103928583A (en) * | 2014-04-29 | 2014-07-16 | 中国科学院上海微系统与信息技术研究所 | Method for preparing GaN monocrystal self-supporting substrate |
| CN107587190A (en) * | 2017-08-14 | 2018-01-16 | 南京大学 | A kind of method for preparing GaN substrate material |
-
2020
- 2020-03-26 CN CN202010223190.9A patent/CN111463325B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519799A (en) * | 2008-02-27 | 2009-09-02 | 中国科学院半导体研究所 | Method for preparing non-polar GaN thick film on sapphire substrate |
| CN101685768A (en) * | 2008-09-23 | 2010-03-31 | 北京大学 | Method for preparing self-supporting mono-crystal gallium nitride substrate |
| CN101431017A (en) * | 2008-12-03 | 2009-05-13 | 南京大学 | Method for improving GaN thick film integrality on sapphire substrate |
| CN102201332A (en) * | 2011-05-08 | 2011-09-28 | 北京燕园中镓半导体工程研发中心有限公司 | Preparation method of GaN substrate |
| CN103647008A (en) * | 2013-12-31 | 2014-03-19 | 中国科学院半导体研究所 | Method for growing semi-polarity GaN (gallium nitride) thick film |
| CN103928583A (en) * | 2014-04-29 | 2014-07-16 | 中国科学院上海微系统与信息技术研究所 | Method for preparing GaN monocrystal self-supporting substrate |
| CN107587190A (en) * | 2017-08-14 | 2018-01-16 | 南京大学 | A kind of method for preparing GaN substrate material |
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