CN102828240A - Method for preparing GaN film material - Google Patents

Method for preparing GaN film material Download PDF

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Publication number
CN102828240A
CN102828240A CN201210316953XA CN201210316953A CN102828240A CN 102828240 A CN102828240 A CN 102828240A CN 201210316953X A CN201210316953X A CN 201210316953XA CN 201210316953 A CN201210316953 A CN 201210316953A CN 102828240 A CN102828240 A CN 102828240A
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gan
film
substrate
nanostructure
preparing
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CN102828240B (en
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修向前
华雪梅
林增钦
张士英
谢自力
张�荣
韩平
陆海
顾书林
施毅
郑有炓
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Nanjing University
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Nanjing University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H01L21/30612—Etching of AIIIBV compounds
    • H01L21/30621—Vapour phase etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials

Abstract

The invention relates to a method for preparing a GaN film material, which comprises the following steps: evaporating a metal nickel(Ni)film on a GaN/sapphire composite substrate, annealing to obtain the nano Ni paticles, then using an inductively coupled plasma etching (ICP) method to etch GaN on the GaN/sapphire composite substrate which is uncovered by Ni and forming the GaN/sapphire composite substrate with a nano structure. The hydride vapor phase epitaxy (HVPE) growth of GaN is carried out on the nano structure composite substrate to obtain the GaN film with low stress and high quality or the self-supporting GaN substrate material. The method of the invention can obtain the GaN film with low stress and high quality.

Description

A kind of method for preparing the GaN thin-film material
Technical field
The present invention relates to the method and the technology of stress in a kind of reduction hydride gas-phase epitaxy (HVPE) growing semiconductor material GaN thin-film material.Especially the method for high quality low-stress GaN film.
Background technology
With GaN and InGaN, AlGaN alloy material is that master's III-V group nitride material (claiming the GaN sill again) is the novel semiconductor material of extremely paying attention in the world in recent years.The GaN sill is the direct band gap semiconductor material with wide forbidden band, has the direct band gap of continuous variable between 1.9-6.2eV, excellent physics, chemicalstability; High saturated electron drift velocity; High-performances such as high breaking down field strength and high heat conductance have important use at aspects such as short wavelength's semiconductor photoelectronic device and high frequency, high pressure, the preparations of high temperature microelectronic device, are used for making such as indigo plant, purple, ultraviolet band luminescent device, sensitive detection parts; High temperature, high frequency, High-Field high power device; Feds, radioprotective device, piezoelectric device etc.
The growth of GaN sill has a variety of methods, like gas phase epitaxy of metal organic compound (MOCVD), HTHP compound body GaN monocrystalline, molecular beam epitaxy (MBE), subliming method and hydride gas-phase epitaxy (HVPE) etc.Because the restriction of the physical properties of GaN sill own, the growth of GaN body monocrystalline has very big difficulty, as yet practicability not.Hydride gas-phase epitaxy can be used for isoepitaxial growth self-supporting GaN substrate owing to have high growth rate and horizontal-vertically extension ratio, causes to pay attention to widely and study.Early stage people mainly adopt hydride gas-phase epitaxy (HVPE) method direct growth GaN sill on Sapphire Substrate, separate again, obtain the GaN substrate material.The outstanding shortcoming of this method is that dislocation desity is very high in the GaN epitaxial film, generally reaches 10 10Cm -2About.Present main method is to adopt methods such as horizontal extension, suspension extension, is aided with HVPE two-forty epitaxy technology growth thick film, at last former substrate is removed, thereby is obtained the lower self-supporting GaN substrate material of dislocation desity.Up to now, the self-supporting GaN substrate that the HVPE growth obtains, dislocation desity is lower than 10 6Cm -2, area has reached 2 inches.But still can not satisfy the demand of practical application far away.
Because GaN can only be grown on foreign substrate such as the substrates such as sapphire, silicon, lattice mismatch and thermal mismatching cause GaN film inside to have big stress, cause GaN base device performance to be difficult to improve.In addition, huge stress can cause GaN thick film and foreign substrate splinter, thereby can't use.Therefore reducing perhaps and eliminate the stress in the GaN thick film, is the important solution of effectively bringing into play GaN material potential.The present invention has provided stress and the method and the technology that obtain self-supporting GaN substrate in reduction hydride gas-phase epitaxy (HVPE) the growing semiconductor material GaN thin-film material.
Summary of the invention
The present invention seeks to: because of existing GaN film growth on foreign substrate such as sapphire etc., lattice mismatch and thermal mismatching can cause the bigger stress of existence in the GaN film.The existence of stress can cause the reduction of GaN sill performance.The present invention proposes to reduce strain method in hydride gas-phase epitaxy (HVPE) the growing semiconductor material GaN thin-film material.
Technical scheme of the present invention is: the method for preparing high quality low-stress GaN thin-film material; Evaporation metal nickel (Ni) film on GaN/ sapphire compound substrate; Nickel (Ni) film GaN/sapphire compound substrate is carried out The high temperature anneal: temperature 600-1000 ℃ in the high quartz stove, time 5-60 minute; Atmosphere is ammonia, flow 100-5000 ml/min; Annealing accomplish the back rapidly feeding nitrogen take out sample with the emptying ammonia after waiting to cool to room temperature; High temperature annealing obtains nanometer Ni particle on GaN/ sapphire compound substrate; Adopt the etching of inductively coupled plasma etching (ICP) mode not by the GaN on the GaN/ sapphire compound substrate of Ni covering then, form the GaN/ sapphire compound substrate of nanostructure;
Hydride gas-phase epitaxy (HVPE) growth of on this nanostructure compound substrate, carrying out GaN obtains low-stress high quality GaN film or self-supporting GaN substrate material.
Under annealing atmosphere and temperature controlled condition, anneal, obtain the Ni particle of different size size.
Ni metallic particles etch rate is slower than GaN etch rate, thereby etches GaN nanostructure (nano-pillar or nano dot).
Described nanostructure GaN/ sapphire compound substrate is placed on carries out transversal epitaxial growth in the HVPE growing system, obtain low-stress GaN film.
Inductively coupled plasma etching (ICP) cavity carries out plasma etching to sample.The ICP parameter is: Cl 2Gas flow be 10-100cm 3/ min; BCl 3Gas flow be 1-50 cm 3/ min; Radio frequency power and ICP power are respectively 50-300W and 100-500W, and pressure is 1E-09 Pa magnitude; Etching time 50-1000S.
The compound substrate of nanometer GaN structure is placed on carries out transversal epitaxial growth (but embodiment referenced patent: " horizontal extension technology growth high-quality gallium nitride film " in the hvpe reactor chamber; Patent No. ZL021113084.1), can obtain high quality low-stress GaN film.
Distribution and the yardstick of the nanostructure GaN that control ICP etching obtains also can be realized the separation certainly between GaN film and the sapphire, thereby obtain low-stress self-supporting GaN substrate material.Realize the separation of GaN thick film above sapphire after the cooling, obtaining the GaN substrate material of high quality low-stress.
Beneficial effect of the present invention is: the method and the technology that have provided stress in a kind of reduction hydride gas-phase epitaxy (HVPE) growing semiconductor material GaN thin-film material.
Description of drawings
Fig. 1 is an embodiment of the invention photo synoptic diagram, the nanometer Ni granule-morphology that metallizing Ni film annealing back forms.Ammonia atmosphere, 800 degree, ammonia flow 800 ml/min.
Fig. 2 is an embodiment of the invention photo synoptic diagram, is the GaN nanostructure pattern that the sample among Fig. 1 forms after the ICP etching.
Embodiment
The inventive method and technology comprise several sections: the physical vapor deposition of metal Ni film on GaN/ sapphire compound substrate; The atmosphere anneal of metal Ni film; Inductively coupled plasma etching GaN/ sapphire compound substrate; The HVPE regrowth of GaN film.
The thickness of metal Ni film and annealing back Ni particulate size, the length dimension of looking the GaN nanostructure is fixed.Thicker Ni film and bigger Ni particle help to obtain vertical and horizontal longer dimension and thicker GaN nanostructure.
One of skill embodiment of the present invention, preparation low-stress GaN film comprises following a few step:
1, the cleaning of GaN/ sapphire compound substrate and processing.
2, GaN/ sapphire compound substrate is put into the physical vapor deposition device reaction chamber, under certain reaction cavity pressure and source metal temperature, can begin the vapor deposition of metal Ni film.The setting of Ni film deposition rate is about 1-2 dust/second, Ni nano film thickness 5-50nm.
3, the sample in the step 2 is put into the high quartz stove and carry out The high temperature anneal.Parameter: temperature 600-1000 ℃, time 5-60 minute; Atmosphere is ammonia, flow 100-5000 ml/min.Etching accomplish the back rapidly feeding nitrogen take out sample with the emptying ammonia after waiting to cool to room temperature.
4, with after the cleaning of the sample in the step 3, put into inductively coupled plasma etching (ICP) cavity, sample is carried out plasma etching.The ICP parameter is: Cl 2Gas flow be 10-100cm 3/ min; BCl 3Gas flow be 1-50 cm 3/ min; Radio frequency power and ICP power are respectively 50-300W and 100-500W, and pressure is 1E-09 Pa magnitude; Etching time 50-1000S.
5, with after the cleaning of the sample in the step 4, put into hydride gas-phase epitaxy equipment, carry out HVPE transversal epitaxial growth GaN.But concrete parameter referenced patent: ZL021113084.1 horizontal extension technology growth high-quality gallium nitride film.
6, sample in the step 5 is taken out, promptly obtain high quality low-stress GaN thin-film material.
7, the parameter among the controlled step 2-5 can realize the separation between GaN film and the sapphire, thereby obtains self-supporting low-stress GaN substrate material.

Claims (4)

1. method for preparing the GaN thin-film material; It is characterized in that evaporation metal nickel (Ni) film on GaN/ sapphire compound substrate; Annealing obtains nanometer Ni particle; Adopt the etching of inductively coupled plasma etching (ICP) mode not by the GaN on the GaN/ sapphire compound substrate of Ni covering then, form the GaN/ sapphire compound substrate of nanostructure; Hydride gas-phase epitaxy (HVPE) growth of on this nanostructure compound substrate, carrying out GaN obtains low-stress high quality GaN film or self-supporting GaN substrate material.
2. the method for preparing the GaN thin-film material according to claim 1 when it is characterized in that metal Ni is annealed into nanometer Ni particle, is annealed under particular atmosphere, specified temp, obtains the Ni particle of different size size.
3. the method for preparing the GaN thin-film material according to claim 1; It is characterized in that in inductively coupled plasma (ICP) the etching GaN technology; Ni metallic particles etch rate is slower than GaN etch rate, thereby etches the GaN nanostructure of nano-pillar or nano dot.
4. according to the described method for preparing the GaN thin-film material of one of claim 1 to 3; It is characterized in that hydride gas phase epitaxial growth carries out in the technology of transversal epitaxial growth; The GaN/ sapphire compound substrate of nanostructure is placed on carries out transversal epitaxial growth in the HVPE growing system, obtain low-stress GaN film.
CN201210316953.XA 2012-08-31 2012-08-31 A kind of method preparing GaN film material Active CN102828240B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014032468A1 (en) * 2012-08-31 2014-03-06 南京大学 Method for preparing gan film material
CN109023515A (en) * 2018-09-03 2018-12-18 南京大学 Prepare GaN substrate from separation method
CN109371462A (en) * 2018-12-05 2019-02-22 石家庄铁道大学 Epitaxial growth organic metal halide perovskite monocrystal thin films preparation method
CN113013731A (en) * 2021-02-19 2021-06-22 苏州科技大学 Flexible electric pumping ZnO nanowire laser array structure and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014032468A1 (en) * 2012-08-31 2014-03-06 南京大学 Method for preparing gan film material
CN109023515A (en) * 2018-09-03 2018-12-18 南京大学 Prepare GaN substrate from separation method
CN109371462A (en) * 2018-12-05 2019-02-22 石家庄铁道大学 Epitaxial growth organic metal halide perovskite monocrystal thin films preparation method
CN113013731A (en) * 2021-02-19 2021-06-22 苏州科技大学 Flexible electric pumping ZnO nanowire laser array structure and preparation method thereof
CN113013731B (en) * 2021-02-19 2023-12-12 苏州科技大学 Flexible electric pumping ZnO nanowire laser array structure and preparation method thereof

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WO2014032468A1 (en) 2014-03-06

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