JPS63103894A - Growing of gallium nitride crystal - Google Patents
Growing of gallium nitride crystalInfo
- Publication number
- JPS63103894A JPS63103894A JP24849286A JP24849286A JPS63103894A JP S63103894 A JPS63103894 A JP S63103894A JP 24849286 A JP24849286 A JP 24849286A JP 24849286 A JP24849286 A JP 24849286A JP S63103894 A JPS63103894 A JP S63103894A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- gallium
- teg
- low
- growth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 14
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims abstract 6
- 238000000034 method Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012159 carrier gas Substances 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は窒化ガリウム結晶の成長方法、更に詳しくは成
長の低温化に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for growing gallium nitride crystals, and more particularly to lowering the growth temperature.
［従来の技術］
従来、窒化ガリウム（ＧａＮ）結晶を有機金属気相成長
法（ＭＯＣＶＤ法）で作成する場合、窒素原料にはアン
モニア（ＮＨ３）、ガリウム原料にはトリメチルガリウ
ム（Ｇａ （ＣＨ３）３．以下ＴＭＧと略す）が主に用
いられて来た。しかし、ＮＨ３は低温での分解効率が低
く窒素の供給効率が悪いので、ＮＨ３に代え、分解効率
の高いヒドラジン（Ｎ２ Ｈ４）を用いてＧａＮの成長
を低温化する試み−がなされている（アプライド・フィ
ツクス・レターズ４８．１４４９−１４５１ （１９８
６））。[Prior Art] Conventionally, when creating gallium nitride (GaN) crystals by metal organic chemical vapor deposition (MOCVD), ammonia (NH3) is used as a nitrogen raw material, and trimethylgallium (Ga (CH3)3) is used as a gallium raw material. (hereinafter abbreviated as TMG) has been mainly used. However, since NH3 has low decomposition efficiency at low temperatures and poor nitrogen supply efficiency, attempts have been made to replace NH3 with hydrazine (N2H4), which has high decomposition efficiency, to lower the temperature for GaN growth (Applied).・Fix Letters 48.1449-1451 (198
6)).
［発明が解決しようとする問題点］
しかし、Ｎ２ Ｈ４を用いることにより低Ｖ族元素／■
族元素（Ｖ’／ＩＩＩ）化生、すなわち、窒素原料の供
給を少なくすることは可能であるが、低温化の面での効
果は以下に述べるように小さい。すなわち、ＴＭＧ−Ｎ
Ｈ３、ＴＭＧ−Ｎ２ Ｈ４系原料でのＧａＮの成長速度
の温度依存性はそれぞれ第２図の（ａ）および（ｂ）で
示され、はぼ同じと見なすことができる。これはＧａＮ
の成長にとっては、窒素原料の分解以上にＱａ原料有機
金属（この場合ＴＭＧ）の分解が重要であることを示し
ていると考えられる。[Problems to be solved by the invention] However, by using N2 H4, low group V elements/■
Although it is possible to perform group element (V'/III) metamorphosis, that is, to reduce the supply of nitrogen raw material, the effect in terms of lowering the temperature is small as described below. That is, TMG-N
The temperature dependence of the growth rate of GaN in H3, TMG-N2, and H4-based raw materials is shown in FIG. 2 (a) and (b), respectively, and can be considered to be almost the same. This is GaN
This seems to indicate that the decomposition of the organic metal Qa raw material (TMG in this case) is more important than the decomposition of the nitrogen raw material for the growth of Qa.
なお第２図において、ＴＭＧ流量は０．２ｃｃ／ｍｉｎ
、ＮＨ３流量は３００ｃｃ／ｍｉｎ 、 Ｎ２ Ｈ４流
量は２ｃｃ／ｍｉｎ 、仝流量は３．Ｑ／ｍｉｎ、圧力
は１００丁ｏｒｒ 、平均流速は１５ｃｍ／ｍｉｎとし
た。In Fig. 2, the TMG flow rate is 0.2cc/min.
, the NH3 flow rate is 300cc/min, the N2 H4 flow rate is 2cc/min, and the flow rate is 3. Q/min, the pressure was 100 orr, and the average flow rate was 15 cm/min.
本発明の目的は、上記の系を原料として用いた場合には
不可能であった低ＶＺＩＩＩ比で、かつ低温下でのＧａ
Ｎ結晶の成長方法を１２供することにある。The purpose of the present invention is to produce Ga at a low VZIII ratio and at low temperatures, which was not possible when the above system was used as a raw material.
The object of the present invention is to provide 12 methods for growing N crystals.
［問題点を解決するための手段］
本発明は、窒素原料としてヒドラジンを、ガリウム原料
としてトリエチルカリウム（Ｇａ（Ｃ２Ｈ５）３ 、以
下ＴＥＧとＩＩＨ”）を用いることを特徴とする窒化ガ
リウム結晶の成長方法である。[Means for Solving the Problems] The present invention provides a method for growing gallium nitride crystals, characterized in that hydrazine is used as a nitrogen raw material and triethylpotassium (Ga(C2H5)3, hereinafter referred to as "TEG" and "IIH") is used as a gallium raw material. It's a method.
［作 用］
従来のＮＨ３に代えＮ２ Ｈ４を用い、かつ、Ｔ Ｍ
Ｇに代え分ＶＩ一温度の低いＴＥＧを用いることにより
、低Ｖ／ｎｌ比、かつ低温でのＧａＮ結晶成長が可能に
なる。[Function] Using N2 H4 instead of conventional NH3, and T M
By using TEG, which has a low VI temperature, in place of G, it becomes possible to grow GaN crystals at a low V/nl ratio and at low temperatures.
［実施例］ 次に本発明を実施例によって説明する。[Example] Next, the present invention will be explained by examples.
本実施例では、（１１１）Ｂ面ヒ化ガリウム（ＧａＡｓ
）基板上に縦型減圧ＭＯＣＶＤ装置てＧａＮを成長させ
た。第１図はその装置の概略図を示したものでおる。有
機洗浄および化学的エツチングを行なったＧａＡｓ基板
７を第１図のカーボンサセプタ１上に載せる。Ｔ Ｅ
Ｇ ２およびＮ２ Ｈ４３はともに２０℃に保温して飽
和蒸気圧を一定に保持し、ト］２でバブルし、Ｈ２をキ
ャリアガスとして反応管４内に供給した。ＴＥＧ流量０
．２ｃｃ／ｍｉ眠Ｎ２ Ｈ４流量は２．０ＣＣ／ｍｉｎ
とし、全流量８．ＩＬ’ｍｉｎ、圧力１００Ｔｏｒｒ
、平均流速１５ｃｍ／ｓｅｃとした。なお、反応管から
排出されるガスは図示しないロータリーポンプから排カ
ス処理装置へ送られろ。また図中６は高周波発振器、Ｆ
１〜１６は流量調節器、■１〜ｖ７はバルブ、Ｒは減圧
弁、ＮＶＩおよびＮＶ２は調圧弁を示す。成長に先立ち
、アルシン（ＡＳＨ３）ボンベ５よりＡＳＨ３を流しな
がら６５０℃で１０分間アニールしてＧａＡＳ表面酸化
膜を除去し、続けて３００ ’Ｃから９００ ’Ｃの間
の幾つかの温度で成長を行なった。成長速度は、■リプ
ツメトリから求めたＧａＮ膜厚と成長時間の比から求め
た。In this example, (111) B-plane gallium arsenide (GaAs
) GaN was grown on the substrate using a vertical low pressure MOCVD apparatus. FIG. 1 shows a schematic diagram of the device. A GaAs substrate 7 that has been subjected to organic cleaning and chemical etching is placed on the carbon susceptor 1 shown in FIG. T E
Both G 2 and N 2 H43 were kept at 20° C. to maintain a constant saturated vapor pressure, bubbled with H 2 , and supplied into the reaction tube 4 with H 2 as a carrier gas. TEG flow rate 0
．． 2cc/mi N2 H4 flow rate is 2.0CC/min
and the total flow rate is 8. IL'min, pressure 100Torr
, and an average flow rate of 15 cm/sec. Incidentally, the gas discharged from the reaction tube is sent to the waste treatment device from a rotary pump (not shown). Also, 6 in the figure is a high frequency oscillator, F
1 to 16 are flow rate regulators, 1 to v7 are valves, R is a pressure reducing valve, and NVI and NV2 are pressure regulating valves. Prior to growth, the GaAS surface oxide film was removed by annealing at 650°C for 10 minutes while flowing ASH3 from an arsine (ASH3) cylinder 5, and then growth was performed at several temperatures between 300'C and 900'C. I did it. The growth rate was determined from the ratio of the GaN film thickness determined from lipometry and the growth time.
第３図にＴＥＧ−Ｎ２ Ｈ４系原料を用いた場合のＧａ
Ｎ成長速度の温度依存性を示す。比較のため第２図に示
した丁ＭＧ−Ｎ２Ｈ４系の場合を加えた。図中（ａ）は
ＴＥＧ−Ｎ２ Ｈ４系の場合を、（ｂ）はＴＭＧ−Ｎ２
Ｈ４系の場合を示す。同図より、明らかに１００ ’Ｃ
程度成長が低温化されている。また本実施例のＶ１ｍ比
は１０であり、従来のＮＨ３を用いた成長でのＶ１ｍ比
（１０００以上）に対し２桁低下しても十分に成長する
ことがわかる。Figure 3 shows Ga when using TEG-N2 H4-based raw material.
The temperature dependence of N growth rate is shown. For comparison, the case of the MG-N2H4 system shown in FIG. 2 was added. In the figure, (a) shows the case of TEG-N2 H4 system, and (b) shows the case of TMG-N2.
The case of H4 system is shown. From the same figure, it is clear that 100'C
The degree of growth is lowered. Further, the V1m ratio of this example is 10, which indicates that sufficient growth can be achieved even if the V1m ratio is lowered by two digits compared to the conventional growth using NH3 (1000 or more).
［発明の効果］
本発明によればＧａＮ成長において低Ｖ１ｍ比化および
低温化が実現可能であり、表面弁ｖｆ４温度の低い■−
■化合物半導体上にも損傷を与えずに成長を行なうこと
ができる。[Effects of the Invention] According to the present invention, it is possible to achieve a lower V1m ratio and lower temperature in GaN growth, and the surface valve vf4 temperature is lower.
(2) Growth can be performed on compound semiconductors without causing damage.
第１図は本発明の成長方法を説明するための一実施例に
用いた装置の概念図、第２図は従来のＴＭＧ−ＮＨ３系
およびＴＭＧ−Ｎ２Ｈ４系を用いた場合の成長速度の温
度依存性を表す図、第３図は本発明によるＴＥＧ−Ｎ２
Ｈ４系のＧａＮ成長速度の温度依存性を表す図でおる
。
１・・・カーボンサセプタ ２・・・ＴＥＧ３・・・Ｎ
２１」４ ４・・・反応管５・・・ＡＳＨ３ボン
ベ ６・・・高周波発振器７・・・ＧａＡｓ基板
Ｆ１〜Ｆ６・・・流量調節器Ｖ１〜ｖ７・・・バルブ
Ｒ・・・減圧弁ＮＶＩ 、 ＮＶ２ ・ｌ［Ｅ
弁
代理人弁理士 舘 野 千恵子
退歿Ｔ（’Ｃ）
第２図Figure 1 is a conceptual diagram of an apparatus used in an example for explaining the growth method of the present invention, and Figure 2 is a diagram showing the temperature dependence of growth rate when using the conventional TMG-NH3 system and TMG-N2H4 system. Figure 3 is a diagram showing the characteristics of TEG-N2 according to the present invention.
This is a diagram showing the temperature dependence of H4-based GaN growth rate. 1...Carbon susceptor 2...TEG3...N
21" 4 4... Reaction tube 5... ASH3 cylinder 6... High frequency oscillator 7... GaAs substrate
F1-F6...Flow rate regulator V1-v7...Valve R...Pressure reducing valve NVI, NV2 ・l[E
Patent Attorney Chieko Tateno Retires T('C) Figure 2
Claims (1)
てトリエチルガリウムを用いることを特徴とする窒化ガ
リウム結晶の成長方法。(1) A method for growing gallium nitride crystals, characterized in that hydrazine is used as a nitrogen raw material and triethylgallium is used as a gallium raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24849286A JPS63103894A (en) | 1986-10-21 | 1986-10-21 | Growing of gallium nitride crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24849286A JPS63103894A (en) | 1986-10-21 | 1986-10-21 | Growing of gallium nitride crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63103894A true JPS63103894A (en) | 1988-05-09 |
Family
ID=17178969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24849286A Pending JPS63103894A (en) | 1986-10-21 | 1986-10-21 | Growing of gallium nitride crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63103894A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100319389B1 (en) * | 1999-06-15 | 2002-01-09 | 김충섭 | Organogallium compound, process for the preparation thereof and preparation of gallium nitride film using same |
| EP2086003A2 (en) | 2008-02-01 | 2009-08-05 | Sumitomo Electric Industries, Ltd. | Method of growing group III-V compound semiconductor, and method of manufacturing light-emitting device and electronic device |
| CN102560633A (en) * | 2007-10-05 | 2012-07-11 | 应用材料公司 | Method for depositing group III/V compounds |
| US8236103B2 (en) | 2002-02-15 | 2012-08-07 | Showa Denko K.K. | Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623957A (en) * | 1979-08-01 | 1981-03-06 | Stork Amsterdam | Transporting apparatus for heat treatment |
-
1986
- 1986-10-21 JP JP24849286A patent/JPS63103894A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623957A (en) * | 1979-08-01 | 1981-03-06 | Stork Amsterdam | Transporting apparatus for heat treatment |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100319389B1 (en) * | 1999-06-15 | 2002-01-09 | 김충섭 | Organogallium compound, process for the preparation thereof and preparation of gallium nitride film using same |
| US8236103B2 (en) | 2002-02-15 | 2012-08-07 | Showa Denko K.K. | Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer |
| CN102560633A (en) * | 2007-10-05 | 2012-07-11 | 应用材料公司 | Method for depositing group III/V compounds |
| CN102560633B (en) * | 2007-10-05 | 2015-11-25 | 应用材料公司 | For the method for depositing group III/V compounds |
| EP2086003A2 (en) | 2008-02-01 | 2009-08-05 | Sumitomo Electric Industries, Ltd. | Method of growing group III-V compound semiconductor, and method of manufacturing light-emitting device and electronic device |
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