JPS64809B2 - - Google Patents
Info
- Publication number
- JPS64809B2 JPS64809B2 JP58042397A JP4239783A JPS64809B2 JP S64809 B2 JPS64809 B2 JP S64809B2 JP 58042397 A JP58042397 A JP 58042397A JP 4239783 A JP4239783 A JP 4239783A JP S64809 B2 JPS64809 B2 JP S64809B2
- Authority
- JP
- Japan
- Prior art keywords
- alkoxide
- reaction system
- semi
- insulating
- 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.)
- Expired
Links
- 150000004703 alkoxides Chemical class 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000001947 vapour-phase growth Methods 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4485—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation without using carrier gas in contact with the source material
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
Description
【発明の詳細な説明】
（技術分野）
この発明は化合物半導体のエピタキシヤル成長
法に関するもので、詳しくは、族の有機金属と
族の水素化物を用いる気相成長法（以下MO−
CVD法という）において、半絶縁性結晶を成長
させる方法に関するものである。Detailed Description of the Invention (Technical Field) The present invention relates to a method for epitaxial growth of compound semiconductors, and more particularly, to a method for epitaxial growth of compound semiconductors.
It relates to a method for growing semi-insulating crystals in the CVD method.
（従来技術）
GaAsなどの−族化合物半導体は、Cr，
Fe，Ｖ，Ｏなどの深い準位をつくる原子を結晶
中に添加すると、電子または正孔が補償されて半
絶縁性の結晶が得られる。GaAsの基板では、
Cr，CrとＯなどの添加による半絶縁性基板が市
販されている。AsCl3またはHClとAsH3を用い
た従来のハライド系の気相成長においても、反応
系内の基板の上流にFe，Ｖなどの金属をおいて、
これを塩化物の形で基板まで輸送して添加した
り、CrO2Cl2を系に導入することなどによつて半
絶縁性成長層を得ている。しかしながら、MO−
CVD法による場合は、一般に系内にClを導入し
ないために、Fe，Ｖなどの金属を系内に入れて
も塩化物となつて基板まで達して添加されること
はなく、したがつて、添加原子は気相の状態で反
応系内に導入しなければならない。(Prior art) - group compound semiconductors such as GaAs are Cr,
When atoms such as Fe, V, and O that create deep levels are added to the crystal, electrons or holes are compensated for, resulting in a semi-insulating crystal. For GaAs substrates,
Semi-insulating substrates with additions of Cr, Cr and O, etc. are commercially available. Even in conventional halide vapor phase growth using AsCl 3 or HCl and AsH 3 , metals such as Fe and V are placed upstream of the substrate in the reaction system.
A semi-insulating growth layer is obtained by transporting this in the form of chloride to the substrate and adding it, or by introducing CrO 2 Cl 2 into the system. However, MO−
When using the CVD method, Cl is generally not introduced into the system, so even if metals such as Fe and V are introduced into the system, they do not become chlorides and reach the substrate and are added. The additive atoms must be introduced into the reaction system in a gas phase.
MO−CVD法による場合、ヘキサカーボニー
ルクロミウムを昇華させて反応系内に導入するこ
とにより、Crを添加した半絶縁性のエピタキシ
ヤル層を得た例はある。 In the case of the MO-CVD method, there are examples in which a semi-insulating epitaxial layer doped with Cr was obtained by sublimating hexacarbonylchromium and introducing it into the reaction system.
しかし、Crは、添加された結晶中で熱処理な
どによつて動きやすい性質がある。そこで、MO
−CVD法においても、比較的動きにくいＶまた
はＶとＯなどの添加が望ましいが、これについて
は行われていない。 However, Cr tends to move easily in the added crystal due to heat treatment or the like. Therefore, M.O.
- Even in the CVD method, it is desirable to add V or V and O, which are relatively immobile, but this has not been done.
（発明の目的・構成）
そこで、本発明者は上記の要望を満足するため
に多数の試験研究を行つた結果、Ｖのアルコオキ
サイドを気相で反応系に導入することにより、
MO−CVD法によつてもＶとＯの添加が可能に
なることを見出し、この発明に至つた。(Objective/Structure of the Invention) Therefore, as a result of conducting numerous tests and studies in order to satisfy the above-mentioned needs, the present inventors found that by introducing V alkoxide into the reaction system in the gas phase,
It was discovered that V and O can be added also by the MO-CVD method, leading to the present invention.
すなわち、この発明は、族の有機金属と族
の水素化物を原料として用いる気相成長におい
て、バナジウムＶのアルコオキサイドを反応系に
導入することにより、ＶとＯを成長層に添加して
半絶縁性の成長層を得ることを特徴とする化合物
半導体のエピタキシヤル成長法であり、MO−
CVD法によつてもＶとＯの添加を可能にして、
高品質の半絶縁性エピタキシヤル成長法を得るこ
とを目的とする。 In other words, this invention introduces an alkoxide of vanadium V into the reaction system in vapor phase growth using a group organic metal and a group hydride as raw materials, thereby adding V and O to the growth layer to form a semi-insulating layer. This is an epitaxial growth method for compound semiconductors, which is characterized by obtaining a growth layer of MO-
It is also possible to add V and O by CVD method,
The aim is to obtain a high quality semi-insulating epitaxial growth method.
（実施例） 以下この発明の実施例を説明する。(Example) Examples of the present invention will be described below.
Ｖのアルコオキサイドはトリメトキシバナジル
VO（CH3）3、トリエトキシバナジルVO
（OC2H5）3など何種類あり、常温近傍で固体また
は液体である。固体の場合は昇華により、また液
体の場合は第１図に示すような通常の気化器を用
いて気相で反応系に導入する。 The alkoxide of V is trimethoxyvanadyl
VO(CH3) 3 , triethoxyvanadylVO
There are several types, such as (OC 2 H 5 ) 3 , which are solid or liquid at around room temperature. In the case of a solid, it is introduced into the reaction system by sublimation, and in the case of a liquid, it is introduced into the reaction system in a gas phase using an ordinary vaporizer as shown in FIG.
第１図において、１は容器、２はキヤリアガス
の入口、３は液体のＶのアルコオキサイドたとえ
ばVO（OC2H5）3、４はＶのアルコオキサイドを
含む気体の出口であり、この出口４からの気体を
MO−CVD法の反応系に導入する。すると、結
晶成長を行つている高温部で分解して、Ｖと一部
のＯが結晶中に添加され、他はメタン、エタンな
どの気体となつて反応系から排気される。 In FIG. 1, 1 is a container, 2 is an inlet for a carrier gas, 3 is a liquid V alkoxide, for example, VO(OC 2 H 5 ) 3 , and 4 is an outlet for a gas containing a V alkoxide. gas from
Introduced into the reaction system of MO-CVD method. Then, it decomposes in the high-temperature part where the crystal is growing, and V and some O are added to the crystal, while the rest becomes gases such as methane and ethane and is exhausted from the reaction system.
常温近傍で固体のＶのアルコオキサイドの場合
たとえばVO（OCH3）3は昇華によつて反応系に導
入するが、このためには第１図に示す気化器の液
体のＶのアルコオキサイドのかわりに固体のＶの
アルコオキサイドを入れるか、または第２図に示
すように、容器５の中に、固体のＶのアルコオキ
サイド６をフイルタ７でとじ込め、入口８から、
キヤリアガスを導入して出口９からＶのアルコオ
キサイドを含む気体を反応系に導入する。 In the case of a V alkoxide that is solid near room temperature, for example, VO(OCH 3 ) 3 is introduced into the reaction system by sublimation. 2, or as shown in FIG. 2, solid V alkoxide 6 is contained in the container 5 with a filter 7, and then from the inlet 8,
A carrier gas is introduced, and a gas containing V alkoxide is introduced into the reaction system from outlet 9.
なお、常温近傍で液体の場合も、固体の場合
も、Ｖのアルコオキサイドの導入量を制御するに
は、これらの容器の温度および容器を通すキヤリ
アガスの量を制御すればよい。 The amount of V alkoxide to be introduced can be controlled by controlling the temperature of these containers and the amount of carrier gas passed through the containers, whether the V alkoxide is liquid or solid near room temperature.
以上説明したように一実施例では、Ｖのアルコ
オキサイドをMO−CVD法の反応系に導入する
ことにより、成長中の化合物半導体中へＶとＯを
添加することができる。これらの原子はGaAsな
どの−族化合物半導体中で深い準位を形成し
て、伝導度を小さくする。このため、もとの結晶
の伝導を補償するに充分なだけの深い準位を形成
する量のＶのアルコオキサイドを添加すれば、半
絶縁性エピタキシヤル成長層を得ることができ
る。また、GaAsの場合は、MO−CVDによる何
も添加していない結晶中のドナとアクセプタの和
が〜1015cm-3程度の高純度結晶が得られるので、
これを補償するにはわずかな量のＶのアルコオキ
サイドを添加すればよく、不純物の少い高品質の
半絶縁性結晶を得ることができるという利点があ
る。 As explained above, in one embodiment, V and O can be added to a growing compound semiconductor by introducing a V alkoxide into the reaction system of the MO-CVD method. These atoms form deep levels in − group compound semiconductors such as GaAs, reducing conductivity. Therefore, a semi-insulating epitaxially grown layer can be obtained by adding an amount of V alkoxide to form a level deep enough to compensate for the conduction of the original crystal. In addition, in the case of GaAs, a high-purity crystal with a sum of donor and acceptor of approximately 10 15 cm -3 can be obtained by MO-CVD without any additives.
To compensate for this, it is sufficient to add a small amount of V alkoxide, which has the advantage that a high quality semi-insulating crystal with few impurities can be obtained.
（発明の効果）
以上詳述したようにこの発明の方法によれば、
Ｖのアルコオキサイドを気相で反応系に導入する
ことにより、MO−CVD法によつてもＶとＯの
添加を可能にして、高品質の半絶縁性エピタキシ
ヤル成長層を得ることができる。この発明の方法
は、FETのバツフア層、イオン打込み用基板な
どの製造方法に利用することができる。(Effect of the invention) As detailed above, according to the method of this invention,
By introducing V alkoxide into the reaction system in the gas phase, V and O can be added even by MO-CVD, and a high quality semi-insulating epitaxial growth layer can be obtained. The method of the present invention can be used in manufacturing methods for FET buffer layers, ion implantation substrates, and the like.
第１図および第２図はこの発明の化合物半導体
のエピタキシヤル成長法の一実施例を説明するた
めの図で、第１図は常温近傍で液体のＶのアルコ
オキサイドを導入するための気化器を示す図、第
２図は常温近傍で固体のアルコオキサイドを導入
するための気化器を示す図である。
１……容器、２……キヤリアガスの入口、３…
…液体のＶのアルコオキサイド、４……出口、５
……容器、６……固体のＶのアルコオキサイド、
７……フイルタ、８……入口、９……出口。
1 and 2 are diagrams for explaining an embodiment of the compound semiconductor epitaxial growth method of the present invention, and FIG. 1 shows a vaporizer for introducing liquid V alkoxide near room temperature. FIG. 2 is a diagram showing a vaporizer for introducing solid alkoxide near room temperature. 1... Container, 2... Carrier gas inlet, 3...
...liquid V alkoxide, 4...outlet, 5
...Container, 6...Solid V alkoxide,
7...filter, 8...inlet, 9...exit.
Claims (1)
て用いる気相成長において、バナジウムＶのアル
コオキサイドを反応系に導入することにより、Ｖ
とＯを成長層に添加して半絶縁性の成長層を得る
ことを特徴とする化合物半導体のエピタキシヤル
成長法。In vapor phase growth using Group 1 organic metals and Group hydrides as raw materials, by introducing vanadium V alkoxide into the reaction system, V
An epitaxial growth method for a compound semiconductor, characterized in that a semi-insulating growth layer is obtained by adding O and O to the growth layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58042397A JPS59169123A (en) | 1983-03-16 | 1983-03-16 | Epitaxial growth of compound semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58042397A JPS59169123A (en) | 1983-03-16 | 1983-03-16 | Epitaxial growth of compound semiconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59169123A JPS59169123A (en) | 1984-09-25 |
| JPS64809B2 true JPS64809B2 (en) | 1989-01-09 |
Family
ID=12634928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58042397A Granted JPS59169123A (en) | 1983-03-16 | 1983-03-16 | Epitaxial growth of compound semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59169123A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598766B2 (en) | 2012-05-27 | 2017-03-21 | Air Products And Chemicals, Inc. | Vessel with filter |
-
1983
- 1983-03-16 JP JP58042397A patent/JPS59169123A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59169123A (en) | 1984-09-25 |
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