CN104993012A - Preparation method of large-size nonpolar A-side GaN self-supporting substrate - Google Patents

Preparation method of large-size nonpolar A-side GaN self-supporting substrate Download PDF

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Publication number
CN104993012A
CN104993012A CN201510270779.3A CN201510270779A CN104993012A CN 104993012 A CN104993012 A CN 104993012A CN 201510270779 A CN201510270779 A CN 201510270779A CN 104993012 A CN104993012 A CN 104993012A
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substrate
gan
face
preparation
nonpolar
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CN104993012B (en
Inventor
李辉杰
杨少延
魏鸿源
赵桂娟
汪连山
李成明
刘祥林
王占国
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Institute of Semiconductors of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1828Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a preparation method of a large-size nonpolar A-side GaN self-supporting substrate, and belongs to the field of photoelectronic device preparation. Compared with the prior art, the preparation method comprises steps of forming a mask film on a substrate epitaxial growth surface; allowing the ask layer to form a graph structure via photoetching and etching technique; then growing a nonpolar A-side GaN thick film; removing the mask layer via GaN horizontal integration or corrosion so as to form a porous structure at the bottom of the GaN thick film; and stripping the GaN thick film from the substrate via the corrosion method, thereby obtaining the nonpolar A-side GaN self-supporting substrate. According to the invention, the A-side GaN substrate in large size can be easily prepared; during the process for stripping the A-side GaN thick film from the substrate, a complex and expensive laser stripping device is not required; and the preparation method is simple in technique, lower in cost and easy to produce and use in large scale.

Description

The preparation method of large scale nonpolar A face GaN self-supported substrate
Technical field
The invention belongs to the preparation field of opto-electronic device, be specifically related to the technology of preparing of a kind of large scale nonpolar A face GaN self-supported substrate.
Background technology
Be that the iii-v nitride semi-conductor material of representative has been widely used in and prepares opto-electronic device, as light-emitting diode, semiconductor laser and photodetector etc. with GaN.But, GaN base device architecture is mainly prepared along C axle orientation (i.e. [0001] crystal orientation), cause along C to the piezoelectricity and spontaneous polarization existed producing larger internal electric field at device inside, cause electronics in quantum well to be separated with hole wave functions, and then cause the photoelectric conversion efficiency of device to decline.For eliminating polarity effect to the adverse effect of device photoelectric conversion efficiency, a kind of method of extensive employing prepares the GaN base device architecture of non polarity A side (i.e. (1120) crystal face).A face GaN base device architecture is vertical with polarized electric field direction, there is not the component of polarized electric field along device growth direction, thus not by the impact of polarity effect.
But current A face GaN material is mainly in foreign substrate, as at R surface sapphire substrate Epitaxial growth.Character mismatch between foreign substrate and epitaxial loayer and thermal mismatching can introduce a large amount of defects, as dislocation and stacking fault etc. in epitaxial loayer.In the GaN epitaxial layer of a kind of A of minimizing face, the Perfected process of defect concentration is the GaN self-supported substrate Epitaxial growth material at non polarity A side.But the technology of preparing of non-polar GaN self-supported substrate is also ripe far away, existing non-polar GaN self-supported substrate obtains along non-polar plane cutting primarily of polarity C face GaN self-supported substrate, its size is less and cost is higher, is difficult to realize large-scale production and application.For obtaining large-sized non-polar GaN substrate, conventional approach is at grown on foreign substrates non-polar GaN thick film material, then non-polar GaN thick film and substrate is peeled off by laser-stripping method, obtains the non-polar GaN substrate of self-supporting.But this kind of method needs the most expensive complicated laser lift-off equipment on the one hand, cost is higher; Can produce the very large gas of pressure bottom GaN thick film on the other hand in laser lift-off process, cause GaN thick film cracked, rate of finished products is not high.
Summary of the invention
The object of the invention is to consider the problems referred to above and the preparation method of a kind of with low cost, surfacing, crystal mass is high, rate of finished products is high large scale nonpolar A face GaN self-supported substrate is provided.
The core that the method preparing large scale nonpolar A face GaN self-supported substrate provided by the invention is different from prior art is, substrate epitaxial growing surface is formed a mask layer, mask layer is made to form graphic structure by photoetching and etching technics, regrowth non polarity A side GaN thick film subsequently, bottom GaN thick film, pore space structure is formed by GaN horizontal meaders or erosion removal medium mask layer, then adopt caustic solution GaN thick film and substrate to be peeled off, and then obtain non polarity A side GaN self-supported substrate.
The method specifically comprises the steps:
Step 1: at deposited on substrates one mask layer, utilizes photoetching and wet etching or dry etching technology to carve graphic structure on mask layer;
Described substrate is the material that can realize non polarity A side GaN growth, comprises R surface sapphire substrate, A surface sapphire substrate, A face SiC substrate, (100) face Si substrate, (302) face γ-LiAlO 2substrate, A face AlN substrate; Or thickness is non polarity A side GaN, AlN, InN of 10 nanometer-100 microns or the alloy firm of three kinds of materials or thick-film material at above-mentioned Grown.The size of substrate as required, from 1 centimetre to 6 inches or larger size.
Described mask layer is the material being unfavorable for GaN nucleating growth, comprises silica, silicon nitride or the material such as tungsten, molybdenum.The thickness of mask layer is that 20 nanometers are to 20 microns.
Wherein mask layer adopts the technology preparations such as chemical vapour deposition (CVD), plasma reinforced chemical vapour deposition or electron beam evaporation.
The graphic structure wherein carved on mask layer can be ordered arrangement structure, also can random arrangement architecture, in regularly arranged, can be the distribution of the arbitrary plane geometries such as bar shaped, rectangle, hexagon, square, parallelogram, triangle, the repetition period be 100 nanometer-100 microns.
Step 2: use growth technology at the above-mentioned Grown A face GaN thick-film material with mask layer, and make to form pore space structure bottom the GaN thick film of A face;
Described epitaxy technology comprises: the combination of molecular beam epitaxy, metal organic chemical vapor deposition, hydride gas-phase epitaxy or several epitaxy technology, as: first adopt molecular beam epitaxy or metal organic chemical vapor deposition to grow the A face GaN material of 50 nanometer-300 microns, then adopt hydride gas-phase epitaxy to grow the A face GaN material of 10 microns-10 millimeters fast.
The method forming hole bottom the GaN thick film of the described A of making face comprises: the method for spontaneous formation hole or the method for employing wet etching removal mask layer formation hole in the GaN thick film merging process of A face.Wherein wet etching liquid is the chemical reagent can removing mask layer, comprises HF solution, BOE, HF dilution, KOH solution, NaOH solution.
Step 3: carry out chemical wet etching to the A face GaN thick-film material with pore space structure, by itself and substrate desquamation, and then forms non polarity A side GaN self-supported substrate.
The corrosive liquid that described chemical wet etching adopts is the chemical reagent to the selective corrosion of GaN opposed polarity mask, comprise the mixed solution of phosphoric acid solution, sulfuric acid solution, sulfuric acid and phosphoric acid, KOH solution, NaOH solution or other to GaN, there is the corrosive liquid of corrosiveness, corrosive liquid temperature is 10 DEG C-500 DEG C, etching time is 1 minute-1 day, can select to stir corrosive liquid or do not stir in corrosion process.
Dominant mechanism of the present invention and technical characterstic:
1. the corrosive liquid such as phosphoric acid or the KOH aqueous solution is different to the corrosion rate in GaN opposed polarity face, and generally, suffered by the non-polar plane of GaN, corrosiveness is less, and GaN crystal face (i.e. N polar surface) then comparatively fast can be corroded by corrosive liquids such as phosphoric acid or the KOH aqueous solution.Have pore space structure bottom the A face GaN thick film of the present invention's growth, hole always has side to be crystal face or and crystal face in the angle being less than 90 degree, thus can corrode by the corrosive liquid such as phosphoric acid or KOH solution.The surface of A face GaN thick film then not affected by corrosive liquid substantially simultaneously, therefore itself and substrate can be peeled off in the impregnable situation of guarantee A face GaN thick film surface, obtain A face GaN self-supported substrate.
2. the present invention is by the process of A face GaN thick film and substrate desquamation, does not need the laser lift-off equipment of complex and expensive, and only need cheap chemical corrosion liquid, thus cost is lower.
3. the present invention obtains the method for non polarity A side GaN substrate compared to traditional employing cutting, adopt the cheap large scale foreign substrate of commercialization as template, the A face GaN self-supported substrate obtained inherits the size of foreign substrate, can obtain large-sized A face GaN substrate.
Non polarity A side GaN self-supported substrate prepared by the present invention may be used for growing nonpolar iii-v nitride semi-conductor material and prepares photoelectric device, overcomes the impact of polarity effect, has a wide range of applications at photoelectric field.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet preparing non polarity A side GaN self-supported substrate according to the embodiment of the present invention;
Fig. 2 is the non polarity A side GaN self-supported substrate prepared by the embodiment of the present invention, and its thickness is about 100 microns, and lateral dimension is about 1.5cm × 1cm.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
In an embodiment of the present invention, a kind of method preparing non polarity A side GaN self-supported substrate is provided.As shown in Figure 1, the method comprises the following steps:
Step 1: get a substrate, adopts R surface sapphire substrate in the present embodiment;
Other can realize the substrate of A face GaN growth, as A surface sapphire substrate, A face SiC substrate, (100) face Si substrate, (302) face γ-LiAlO 2substrate, A face AlN substrate etc., or the alloy firm of A face GaN, AlN, InN or three kind of the material grown on such substrates or thick-film material, also can adopt;
Step 2: be positioned over by substrate in mask Preparation equipment, deposits certain thickness mask layer;
Mask Preparation equipment comprises chemical vapour deposition (CVD), plasma reinforced chemical vapour deposition or electron beam evaporation, and the present embodiment adopts plasma reinforced chemical vapour deposition equipment; Mask can be the materials such as silica, silicon nitride or tungsten, and the present embodiment selects silica material; The thickness of mask layer be 20 nanometers to 20 microns, the present embodiment adopts 200 nanometers;
Step 3: adopt the method for photoetching and etching to etch certain graphic structure on mask layer;
Graphic structure can be the distribution of the arbitrary plane geometries such as bar shaped, rectangle, hexagon, square, parallelogram, triangle, the present embodiment adopts periodically strip structure, its direction is perpendicular to [0001] crystal orientation of R surface sapphire substrate, and bar is wide 3 microns, and the cycle is 6 microns;
Step 4: prepare GaN thick film on the above-mentioned substrate preparing graphic mask;
The preparation method of GaN thick film can be the combination of molecular beam epitaxy, metal organic chemical vapor deposition, hydride gas-phase epitaxy or several epitaxy technology, adopts metal organic chemical vapor deposition method in the present embodiment; The thickness of GaN thick film is 10 microns-10 millimeters, adopts 100 microns in the present embodiment;
Step 5: carry out wet etching to above-mentioned GaN thick film, removes mask layer, forms hole in the bottom of GaN thick film;
Wherein wet etching liquid comprises: HF solution, BOE, HF dilution, KOH solution, NaOH solution or other can the chemical solution of etching mask, the present embodiment adopts HF dilution;
Step 6: adopt KOH solution to corrode to the above-mentioned A face GaN thick-film material with pore space structure, by itself and substrate desquamation, and then obtain non polarity A side GaN self-supported substrate.
It should be noted that, other can corrode GaN the corrosive agent of crystal face, as the mixed solution of phosphoric acid solution, sulfuric acid solution, sulfuric acid and phosphoric acid, NaOH solution also can adopt.
Fig. 2 is the non polarity A side GaN self-supported substrate prepared by the embodiment of the present invention, and its thickness is about 100 microns, and lateral dimension is about 1.5cm × 1cm.According to the knowledge of the applicant, this is the maximum sized A face GaN self-supported substrate adopting Sapphire Substrate to prepare at present, shows that the method has very large creativeness and feasibility.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a preparation method for large scale nonpolar A face GaN self-supported substrate, its step comprises:
Step 1: at deposited on substrates one mask layer, utilize photoetching and wet etching, or photoetching and dry etching technology carve graphic structure on mask layer;
Step 2: at the above-mentioned Grown A face GaN thick-film material with mask layer, and form pore space structure bottom the GaN thick film of A face;
Step 3: carry out chemical wet etching to the A face GaN thick-film material with pore space structure, by itself and substrate desquamation, and then forms non polarity A side GaN self-supported substrate.
2. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 1, described substrate is R surface sapphire substrate, A surface sapphire substrate, A face SiC substrate, (100) face Si substrate or (302) face γ-LiAlO 2substrate, A face AlN substrate; Or thickness is non polarity A side GaN, AlN, InN of 10 nanometer-100 microns or the alloy material of three at above-mentioned Grown.
3. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 1, described mask material is silica, silicon nitride, tungsten or molybdenum.
4. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 1, described figure is the bar shaped of ordered arrangement structure, rectangle, hexagon, square, parallelogram or triangle, and the repetition period is 100 nanometer-100 microns.
5. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 2, the growing technology of described A face GaN thick film is the combination of molecular beam epitaxy, metal organic chemical vapor deposition, hydride gas-phase epitaxy or above-mentioned several epitaxy technology.
6. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 2, the thickness of described A face GaN thick film is: 10 microns-10 millimeters.
7. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 2, the method forming hole bottom the GaN thick film of A face is the method for spontaneous formation hole in the GaN thick film merging process of A face or adopts wet etching to remove the method for mask layer formation hole.
8. the preparation method of large scale nonpolar A face according to claim 7 GaN self-supported substrate, the corrosive liquid that wherein wet method removes mask layer used is HF solution, BOE, HF dilution, KOH solution or NaOH solution.
9. the preparation method of large scale nonpolar A face according to claim 1 GaN self-supported substrate, wherein in step 3, the corrosive liquid of described chemical corrosion A face GaN thick film is the mixed solution of phosphoric acid solution, sulfuric acid solution, sulfuric acid and phosphoric acid, KOH solution or NaOH solution.
10. the preparation method of large scale nonpolar A face according to claim 9 GaN self-supported substrate, wherein corrosive liquid temperature is 10 DEG C-500 DEG C, and etching time is 1 minute-1 day, can stir corrosive liquid or not stir in corrosion process.
CN201510270779.3A 2015-05-25 2015-05-25 Preparation method of large-size nonpolar A-side GaN self-supporting substrate Expired - Fee Related CN104993012B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107326444A (en) * 2017-07-21 2017-11-07 山东大学 A kind of method that hydro-thermal corrosion porous-substrates grow self-standing gan monocrystalline
CN110517949A (en) * 2019-07-29 2019-11-29 太原理工大学 It is a kind of to utilize SiO2Method as the substrate preparation nonpolarity face a GaN epitaxial layer
CN111223763A (en) * 2020-01-19 2020-06-02 镓特半导体科技(上海)有限公司 Semiconductor structure, self-supporting gallium nitride layer and preparation method thereof
CN112018199A (en) * 2019-05-30 2020-12-01 南京信息工程大学 High-quality nonpolar AlGaN micro-nano composite structure and processing method thereof

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CN102903614A (en) * 2012-08-28 2013-01-30 中国科学院半导体研究所 Method for preparing non-polar A face GaN thin film
CN103682016A (en) * 2012-08-30 2014-03-26 上海华虹宏力半导体制造有限公司 Manufacturing method for GaN epitaxy or substrate

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JP2000286506A (en) * 1999-03-31 2000-10-13 Furukawa Electric Co Ltd:The Gallium nitride light-emitting device
JP2010135859A (en) * 2010-03-17 2010-06-17 Panasonic Electric Works Co Ltd Method of manufacturing semiconductor light emitting device
US20120043578A1 (en) * 2010-08-23 2012-02-23 Su-Hui Lin GaN-Based Light-Emitting Diode and Method for Manufacturing the Same
CN102347214A (en) * 2011-07-06 2012-02-08 德泓(福建)光电科技有限公司 Preparation method for graphical template used for growing thick-film GaN material
CN102903614A (en) * 2012-08-28 2013-01-30 中国科学院半导体研究所 Method for preparing non-polar A face GaN thin film
CN103682016A (en) * 2012-08-30 2014-03-26 上海华虹宏力半导体制造有限公司 Manufacturing method for GaN epitaxy or substrate

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107326444A (en) * 2017-07-21 2017-11-07 山东大学 A kind of method that hydro-thermal corrosion porous-substrates grow self-standing gan monocrystalline
CN112018199A (en) * 2019-05-30 2020-12-01 南京信息工程大学 High-quality nonpolar AlGaN micro-nano composite structure and processing method thereof
CN110517949A (en) * 2019-07-29 2019-11-29 太原理工大学 It is a kind of to utilize SiO2Method as the substrate preparation nonpolarity face a GaN epitaxial layer
CN110517949B (en) * 2019-07-29 2021-05-11 太原理工大学 By using SiO2Method for preparing nonpolar a-plane GaN epitaxial layer as substrate
CN111223763A (en) * 2020-01-19 2020-06-02 镓特半导体科技(上海)有限公司 Semiconductor structure, self-supporting gallium nitride layer and preparation method thereof
CN111223763B (en) * 2020-01-19 2024-04-12 镓特半导体科技(上海)有限公司 Semiconductor structure, self-supporting gallium nitride layer and preparation method thereof

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