JPH04175293A - Method for selective crystal growth - Google Patents
Method for selective crystal growthInfo
- Publication number
- JPH04175293A JPH04175293A JP30497390A JP30497390A JPH04175293A JP H04175293 A JPH04175293 A JP H04175293A JP 30497390 A JP30497390 A JP 30497390A JP 30497390 A JP30497390 A JP 30497390A JP H04175293 A JPH04175293 A JP H04175293A
- Authority
- JP
- Japan
- Prior art keywords
- tantalum oxide
- single crystal
- growth
- gaas
- raw material
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 43
- 230000012010 growth Effects 0.000 title abstract description 24
- 238000000034 method Methods 0.000 title abstract description 16
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 19
- 238000002109 crystal growth method Methods 0.000 claims description 9
- 238000001947 vapour-phase growth Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 14
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000070 arsenic hydride Inorganic materials 0.000 abstract description 8
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 abstract 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 43
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 42
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- MDPILPRLPQYEEN-UHFFFAOYSA-N aluminium arsenide Chemical compound [As]#[Al] MDPILPRLPQYEEN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000700560 Molluscum contagiosum virus Species 0.000 description 1
- -1 P H3 Chemical compound 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 description 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 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ｍ−ｖ族化合物半導体の選択結晶成長方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for selective crystal growth of m-v group compound semiconductors.
従来、ＧａＡｓ （ガリウムヒ素）等の■−ｖ族化合物
半導体の集積化あるいは高性能化のために、選択的に限
定された領域のみにＧａＡｓ等の■−ｖ族化合物半導体
を形成する手法として、選択成長が用いられてきた。Conventionally, in order to integrate or improve the performance of ■-v group compound semiconductors such as GaAs (gallium arsenide), methods have been used to form ■-v group compound semiconductors such as GaAs only in selectively limited areas. Selective growth has been used.
これらの場合、酸化けい素、窒化けい素薄膜面上にＧａ
Ａｓ等の化合物半導体が形成されにくいことを利用し、
酸化けい素、窒化けい素薄膜面とＧａＡｓ単結晶面を用
いて、この酸化けい素、窒化けい素上にＧａＡｓ単結晶
あるいは多結晶を形成せずに、ＧａＡｓ単結晶面上にＧ
ａＡｓ単結晶を形成している。In these cases, Ga is deposited on the silicon oxide or silicon nitride thin film surface.
Taking advantage of the fact that compound semiconductors such as As are difficult to form,
By using a silicon oxide or silicon nitride thin film surface and a GaAs single crystal surface, G is formed on the GaAs single crystal surface without forming a GaAs single crystal or polycrystal on the silicon oxide or silicon nitride.
It forms an aAs single crystal.
しかしながら、上記従来例では非形成面の面積が大きく
なると酸化けい素、窒化けい素等のＧａＡｓ単結晶、多
結晶を形成しない面上にＧａＡｓ単結晶核あるいは多結
晶が形成されてしまう。However, in the conventional example described above, when the area of the non-forming surface becomes large, GaAs single crystal nuclei or polycrystals are formed on the surface where GaAs single crystals or polycrystals such as silicon oxide or silicon nitride are not formed.
本発明の選択結晶成長方法は気相成長法を用いる選択結
晶成長方法において、単結晶あるいは多結晶を形成しな
い非形成面として酸化タンタルを用い、塩素を含む原料
ガスを供給することを特徴とする特
本発明は、選択成長を行う際に、塩素を含む原料ガスを
供給し、単結晶あるいは多結晶を形成しない非形成面と
して、酸化けい素や窒化けい素に比べ、より速くエツチ
ングされる酸化タンタルを用いるものである。The selective crystal growth method of the present invention is a selective crystal growth method using a vapor phase growth method, characterized in that tantalum oxide is used as a non-formation surface where single crystals or polycrystals are not formed, and a raw material gas containing chlorine is supplied. In particular, the present invention supplies raw material gas containing chlorine during selective growth, and uses oxidized oxide, which is etched more quickly than silicon oxide or silicon nitride, as a non-forming surface that does not form single crystals or polycrystals. It uses tantalum.
単結晶あるいは多結晶を形成しない非形成面とする酸化
タンタルをエツチングする塩素を含む原料ガスを供給す
ることにより、非形成面上に単結晶あるいは多結晶が生
ずることを抑制し、選択性を向上できる。また、単結晶
あるいは多結晶を形成しない面は成長中にエツチングさ
れて行くため、酸化タンタルの膜厚を制御することによ
り、選択成長、全面成長を連続的に行うことが可能であ
る。By supplying raw material gas containing chlorine that etches tantalum oxide on the non-forming surface where single crystals or polycrystals are not formed, the formation of single crystals or polycrystals on the non-forming surface is suppressed and selectivity is improved. can. Furthermore, since the surfaces on which single crystals or polycrystals are not formed are etched during growth, by controlling the thickness of the tantalum oxide film, selective growth and full-scale growth can be performed continuously.
本発明の実施態様例を示す。 An example embodiment of the present invention is shown.
第１図に示すように基板表面に単結晶あるいは多結晶を
形成しない非形成面部分に酸化タンタルｌを形成し、単
結晶を形成する部分にＧａＡｓ、 ＩｎＰＳＳｉ。As shown in FIG. 1, tantalum oxide is formed on the surface of the substrate where no single crystal or polycrystal will be formed, and GaAs and InPSSi are formed on the area where the single crystal will be formed.
ＡＡ ＱａＡｓＸＧａＩｎＡｓＰ等の半導体結晶２が露
出した面を形成する。酸化タンタルの形成法としては、
例えばＥＢ（電子線）蒸着法、スパッタ法等を用いる。An exposed surface of semiconductor crystal 2 such as AA QaAsXGaInAsP is formed. The method of forming tantalum oxide is as follows:
For example, an EB (electron beam) evaporation method, a sputtering method, or the like is used.
つぎに、ＭＯＣＶＤ法（有機金属化学気相成長法）ある
いはＶＰＥ法（塩化物気相成長法）等のガス状の原料を
用いた気相成長法を用いて、選択成長を行う。この時、
Ｖ族原料としてＡｓＨ３、ＴＢＡｓ （ターシャルブチ
ルアルシン）、ＴＭＡｓ （トリメチルアルシン）、Ｐ
Ｈ３、ＴＢＰ （ターシャルブチルホスフィン）等を用
いる。また、■族原料としては、ＴＭＧ（トリメチルガ
リウム）、ＴＥＧ（トリエチルカリウム）、ＴＭＡ（ト
リメチルアルミニウム）、ＴＥＡ（トリエチルアルミニ
ウム）、ＴＭＩｎ （）リメチルインジウム）、ＴＥＩ
ｎ （トリエチルインジウム）等の原料が用いられる。Next, selective growth is performed using a vapor phase growth method using a gaseous raw material, such as MOCVD (metal organic chemical vapor deposition) or VPE (chloride vapor phase epitaxy). At this time,
Group V raw materials include AsH3, TBAs (tertiary butylarsine), TMAs (trimethylarsine), P
H3, TBP (tertiary butylphosphine), etc. are used. In addition, as group III raw materials, TMG (trimethylgallium), TEG (triethylpotassium), TMA (trimethylaluminum), TEA (triethylaluminum), TMIn ()limethylindium), TEI
Raw materials such as n (triethyl indium) are used.
これらの原料と同時にＨＣＡガス３を供給し、選択成長
を行うのが望ましい。It is desirable to supply HCA gas 3 simultaneously with these raw materials to perform selective growth.
ＭＯＣＶＤ法を用いて選択成長を行う場合、以下のよう
な条件で行う。When performing selective growth using the MOCVD method, it is performed under the following conditions.
成長温度は一般には５００〜８００°Ｃ１望ましくは５
７０〜７６０℃、最適には６００〜７００°Ｃで行い、
圧力は一般には７６０Ｔｏｒｒ以下、望ましくは１００
Ｔｏｒｒ以下、最適には２０Ｔｏｒｒ以下で行う。また
、Ｖ族原料供給量／■族原料供給量の比は一般には５〜
３００、望ましくは１０〜２００、最適には３０〜１５
０で行い原料とともに供給するＨＣＩの供給モル量の全
供給ガスに占める割合は一般には１〜１１０００ｐｐ、
望ましくは１〜５００ ｐ ｐ ｍ 、最適には５〜ｌ
１００ｐｐとする。The growth temperature is generally 500 to 800°C, preferably 5
Perform at 70-760°C, optimally at 600-700°C,
The pressure is generally below 760 Torr, preferably 100 Torr.
Torr or less, optimally 20 Torr or less. In addition, the ratio of Group V raw material supply/■ Group raw material supply is generally 5 to 5.
300, preferably 10-200, optimally 30-15
The proportion of the molar amount of HCI supplied together with the raw material in the total supply gas is generally 1 to 11000 pp,
Desirably 1-500 ppm, optimally 5-1
It is set to 100pp.
また、ＥＢ蒸着法により酸化タンタルを形成する際、酸
素供給量を変化させた試料を作成し、この後、ＭＯＣＶ
Ｄ法を用いて、結晶形成処理を施し５ｃｍ角の酸化タン
タル上に形成された単結晶核の密度を測定した。この結
果を第２図に示す。これより、酸化タンタルの作成条件
により、酸化タンタル上に形成される単結晶核の数は異
なることが分かる。In addition, when forming tantalum oxide by the EB evaporation method, samples were created with varying oxygen supply amounts, and then MOCV
Using the D method, the density of a single crystal nucleus formed on a 5 cm square tantalum oxide subjected to crystal formation treatment was measured. The results are shown in FIG. This shows that the number of single crystal nuclei formed on tantalum oxide varies depending on the tantalum oxide production conditions.
これは、酸化タンタルの組成により酸化タンタル上に形
成される単結晶核の数が異なることを示していると考え
られる。第２図が極小値を持っていることは、酸素の組
成比が大きい場合には酸化タンタルのエツチングレート
が小さくなりＧａＡｓの形成を抑制することが出来な（
なるためＧａＡｓ単結晶核が増加し、酸素の組成比が小
さい場合には酸化タンタルの表面モホロジーが悪化する
ためにＧａＡｓ単結晶核が増加すると考えられる。ここ
で、ＭＯ（、ＶＤ法を用いた結晶形成処理の条件は、ま
ず、基板温度７６０℃、圧力１００ＴｏｒｒてＡｓＨ３
を６ Ｘ １０−’ｍｏｌｔ／ｍｉｎ、、水素を１０１
／ｍｉｎ、供給し、２０分間表面処理を行う。その後基
板温度７８０℃、圧力１０Ｔｏｒｒて原料ガスとしてＡ
ｓＨ３を４ Ｘ １０−’ｍｏｌ／ｍｉｎ、、ＴＭＧを
１ ｘ １０１０−ｌｌ Ｅ ／ ｍｉｎ、、水素を１
０１！ ／ ｍｉｎ、ＨＣｊ！ガスを２ ｘ １０−５
ｍｏ １． ／ｍ ｉ ｎ 、を２０分供給した。This is considered to indicate that the number of single crystal nuclei formed on tantalum oxide varies depending on the composition of tantalum oxide. The fact that FIG. 2 has a minimum value is because when the oxygen composition ratio is large, the etching rate of tantalum oxide becomes small and the formation of GaAs cannot be suppressed (
Therefore, it is thought that the number of GaAs single crystal nuclei increases, and when the oxygen composition ratio is small, the surface morphology of tantalum oxide deteriorates, so that the number of GaAs single crystal nuclei increases. Here, the conditions for the crystal formation treatment using the MO (VD method) are as follows: first, the substrate temperature is 760°C, the pressure is 100 Torr, and AsH3
6 × 10-'molt/min, 101 hydrogen
/min, and perform surface treatment for 20 minutes. After that, the substrate temperature was 780°C, the pressure was 10 Torr, and A was used as the raw material gas.
sH3 at 4 x 10-'mol/min, TMG at 1 x 1010-ll E/min, hydrogen at 1
01! / min, HCj! 2 x 10-5 gas
mo1. /min for 20 minutes.
また、ＨＣＩ供給量を変化させ、５ｃｍ角の酸化タンタ
ル上に形成されるＧａＡｓ単結晶核の密度変化を測定し
た。また比較のためＳｉ基板を熱酸化処理し得られた５
ｃｍ角の酸化けい素上に形成されたＧａＡｓ単結晶核の
数の変化を酸化タンタルと同時に結晶形成処理を施し調
べた。この結果を第５図に示す。酸化タンタルはＨＣＩ
供給量に対して極小値を持っていることが分かる。これ
はＨＣＩ供給量が少ない場合には酸化タンタルのエツチ
ングレートが小さくなりＧａＡｓの形成を抑制すること
が出来なくなるためＧａＡｓ単結晶核が増加し、ＨＣｊ
７供給量が多い場合にはエツチングレートが大きすぎる
ため、酸化タンタルの表面モホロジーが悪化するために
ＧａＡｓ単結晶核が増加すると考えられる。Furthermore, the density change of GaAs single crystal nuclei formed on a 5 cm square tantalum oxide was measured by changing the amount of HCI supplied. For comparison, a Si substrate was thermally oxidized.
Changes in the number of GaAs single crystal nuclei formed on cm square silicon oxide were investigated by performing crystal formation treatment simultaneously with tantalum oxide. The results are shown in FIG. Tantalum oxide is HCI
It can be seen that it has a minimum value relative to the supply amount. This is because when the amount of HCI supplied is small, the etching rate of tantalum oxide becomes small and the formation of GaAs cannot be suppressed, so the number of GaAs single crystal nuclei increases and HCj
If the supply amount of 7 is large, the etching rate is too high, and it is thought that the surface morphology of tantalum oxide deteriorates and the number of GaAs single crystal nuclei increases.
ここで用いた酸化タンタルはＥＢ蒸着により作成され、
この時の酸素供給量は１０ ｃ ｃ ／ ｍ ｉ ｎ
、である。The tantalum oxide used here was created by EB evaporation,
The oxygen supply amount at this time is 10 cc/min
, is.
また、結晶形成処理はＭＯＣＶＤ法を用いて、まず、基
板温度７６０℃、圧力１００ＴｏｒｒてＡｓＨ３を６
Ｘ １０−’ｍｏｂ／ｍｉｎ、、水素を１０１ ／ ｍ
ｉ ｎ 、供給し、２０分間表面処理を行う。その後
基板温度７８０℃、圧力１０Ｔｏｒｒで原料ガスとして
ＡｓＨ３を４Ｘ１０−’ｍｏｊ！／ｍｉｎ、、ＴＭＧを
ｌＸｌ０−’ｍｏ Ｉ！ ／ｍｉｎ、、水素を１０１
／ｍｉｎ、ＨＣＩ！ガスを２ Ｘ １０−’ｍｏ ！！
／ ｍｉｎ。In addition, the crystal formation process was performed by using the MOCVD method, and first, 6 AsH3 was heated at a substrate temperature of 760°C and a pressure of 100 Torr.
X 10-'mob/min, hydrogen at 101/m
i n , and surface treatment for 20 minutes. After that, AsH3 was used as a raw material gas at a substrate temperature of 780°C and a pressure of 10 Torr. /min,, TMG as lXl0-'mo I! /min,, 101 hydrogen
/min, HCI! 2 X 10-'mo of gas! !
/ min.
を２０分供給した。was supplied for 20 minutes.
〔実施例１〕 本発明の実施例を示す。[Example 1] An example of the present invention is shown.
第３図（ａ）に示すようにｎ型ＡＩ！ ＧａＡｓ ５、
ＧａＡｓ６、ｐ型ＡＩ！ＧａＡｓ７、ｐ型Ａ Ｉ Ｇａ
Ａｓ Ｂを順次成長したｎ型ＧａＡｓ基板４上に酸化タ
ンタル１を１５００人をＥＢ蒸着により蒸着する。ここ
で、ＥＢ蒸着の条件としては、バックグランドを１０−
６Ｔ ｏ ｒ ｒまで真空にし、次に０２を１０ｃｃ／
ｍｉｎ、供給し蒸着した。As shown in Figure 3(a), n-type AI! GaAs 5,
GaAs6, p-type AI! GaAs7, p-type AI Ga
On an n-type GaAs substrate 4 on which AsB was sequentially grown, 1,500 pieces of tantalum oxide 1 were deposited by EB evaporation. Here, the conditions for EB evaporation are that the background is 10-
Vacuum to 6T o r r, then 02 to 10cc/
min, was supplied and deposited.
第３図（ｂ）に示すようにホトリソグラフィにより２０
０μｍピッチで２μｍのラインを抜いたパターンを形成
した。As shown in Figure 3(b), 20
A pattern was formed in which lines of 2 μm were cut out at a pitch of 0 μm.
第３図（Ｃ）に示すようにＩＢＥにより８００μｍのラ
イン部の酸化タンタルを残し、５００μｍのライン部Ｇ
ａＡｓを表面に露出した。ここで、ＩＢＥの条件は、Ｃ
Ｆ４を２０ ｃ ｃ ７ ｍ ｉ ｎ 、 ０２を２ｃ
ｃ／ｍｉｎ。As shown in Figure 3(C), tantalum oxide in the 800 μm line portion was left by IBE, and the line portion G in the 500 μm line portion was removed.
aAs was exposed on the surface. Here, the conditions for IBE are C
F4 is 20 c c 7 min, 02 is 2 c
c/min.
供給し、圧力１０Ｐａ、パワー１００Ｗで２０分間エツ
チングした。Etching was carried out for 20 minutes at a pressure of 10 Pa and a power of 100 W.
第３図（ｄ）に示すようにその後、レジスト１５を取り
去り、表面の清純化を行った。As shown in FIG. 3(d), the resist 15 was then removed to purify the surface.
第３図（ｅ）に示すようにＭＯＣＶＤ法を用いて基板温
度７６０°Ｃ１圧力１００ＴｏｒｒでＡｓＨ３を６ Ｘ
１０−’ｍｏｊ！／ｍｉｎ、、水素を１０１／ｍｉｎ
、、供給し、２０分間表面処理を行う。その後基板温度
７６０°Ｃ１圧力２０Ｔｏｒｒで原料ガスとしてＡｓＨ
３を４ Ｘ Ｉ Ｏ−’ｍｏｊｉ！／ｍｉｎ、、ＴＭＧ
をＩ Ｘ １０−５ｍｏ ｌ ／ ｍｉｎ、、水素を１
０１／ｍｉｎ、、Ｈ（１！ガスを２Ｘ１０’ｍｏｊｌ！
／ ｍ ｉ ｎ 、供給してＧａＡｓ９を選択成長した
（１時間）。As shown in Figure 3(e), AsH3 was 6
10-'moj! /min,, hydrogen 101/min
,, and perform surface treatment for 20 minutes. After that, AsH was used as the raw material gas at a substrate temperature of 760°C and a pressure of 20 Torr.
3 to 4 X I O-'moji! /min,,TMG
I x 10-5 mol/min, hydrogen 1
01/min,,H(1!Gas 2X10'mojl!
/min for selective growth of GaAs9 (1 hour).
非形成面としてＳｉｏ２を用いて、同一条件で成長した
場合、Ｓｉｏ２上にＧａＡｓ単結晶核は５０個／ｃｒｒ
？であったのに対して、酸化タンタル上に形成されたＧ
ａＡｓ単結晶核は２０個／ ｃ ｍ ２であり、選択性
が向上したことが示された。When grown under the same conditions using Sio2 as a non-forming surface, the number of GaAs single crystal nuclei on Sio2 is 50/crr.
? On the other hand, G formed on tantalum oxide
The number of aAs single crystal nuclei was 20/cm2, indicating that the selectivity was improved.
〔実施例２〕 本発明の実施例を示す。[Example 2] An example of the present invention is shown.
第４図（ａ）に示すようにＳ１ドープのｎ型ＧａＡｓ基
板（２Ｘ １０１８ｃｍ−３） ９上に酸化タンタルｌ
を２００人をＥＢ蒸着により蒸着した。ここで、ＥＢ蒸
着の条件としては、バックグランドを１０’Ｔｏｒｒま
で真空にし、次に０２を１０ｃｃ／ｍｉｎ供給し、蒸着
した。As shown in Fig. 4(a), tantalum oxide l is placed on an S1-doped n-type GaAs substrate (2X 1018 cm-3).
200 people were deposited by EB deposition. Here, the conditions for the EB vapor deposition were as follows: the background was vacuumed to 10' Torr, and then 02 was supplied at 10 cc/min for vapor deposition.
第４図（ｂ）に示すようにホトリソグラフィにより２０
０μｍピッチで２μｍのラインを残したパターンを形成
した。As shown in FIG. 4(b), 20
A pattern was formed with a pitch of 0 μm and lines of 2 μm remaining.
第４図（Ｃ）に示すようにＩＢＥにより２μｍのライン
部以外の酸化タンタルを取り去り、ＧａＡｓを表面に露
出させる。ここで、ＩＢＥの条件は、ＣＦ４を２０ｃｃ
／ｍｉｎ、、０□を２ｃｃ／ｍｉｎ、供給し、圧力１０
Ｐａ、パワー１００Ｗで３分間エツチングする。As shown in FIG. 4(C), tantalum oxide other than the 2 μm line portion is removed by IBE to expose GaAs on the surface. Here, the conditions for IBE are 20cc of CF4.
/min,, 0□ is supplied at 2cc/min, and the pressure is 10
Etch for 3 minutes at Pa and power of 100W.
第４図（ｄ）に示すようにその後、レジスト１５を取り
去り、表面の清純化を行う。As shown in FIG. 4(d), the resist 15 is then removed and the surface is purified.
第４図（ｅ）に示すようにＭＯＣＶＤ法を用いて基板温
度７６０℃、圧力１００ＴｏｒｒでＡｓＨ３を６ Ｘ
１０−’ｍｏｆ／ｍｉｎ、、水素１０ｊ！／ｍｉｎ、供
給し、２０分間表面処理を行った。その後基板温度７６
０℃、圧力２０Ｔｏｒｒで原料ガスとしてＡｓＨ３を４
Ｘ １０−’ｍｏ１／ｍｉｎ、、ＴＭＧをＩ Ｘ １
０−６ｍｏ ｉ／ ｍｉｎ、、水素を１０ｆ／ｍｉｎ、
、ＨＣｌガスを２Ｘ１０−’ｍｏｌ／ｍｉｎ、、ＤＥＺ
ｎをＩ Ｘ １０−６ｍｏ Ｉ！ ／ ｍｉｎ、供給し
てｐ型ＧａＡｓ （Ｉ Ｘ １０”ｃｍ＝） １１を選
択成長した（１時間）。As shown in FIG. 4(e), AsH3 was 6
10-'mof/min,, hydrogen 10j! /min, and surface treatment was performed for 20 minutes. Then the substrate temperature 76
AsH3 was used as the source gas at 0°C and 20 Torr.
X 10-'mo1/min,, TMG I X 1
0-6mo i/min, hydrogen 10f/min,
, HCl gas at 2X10-'mol/min, DEZ
n to I x 10-6mo I! p-type GaAs (I x 10"cm=) 11 was selectively grown (1 hour).
次に、連続的にＤＥＺｎをＳｉＨ４に切り換えて、Ｉ
Ｘ １０−’ｍｏ ｌ！ ／ ｍ ｉｎ 、供給し、ｎ
型ＧａＡｓ（Ｉｘｌσ８ｃｍ−５）１２を形成した（３
０分）。Next, continuously switch DEZn to SiH4 and
X 10-'mol! /min,supply,n
type GaAs (Ixlσ8cm-5)12 was formed (3
0 minutes).
第４図（ｆ）に示すように次に、ＨＣＩガスの供給を止
め、ＴＭＡ （１−リンチルガリウム）を３ Ｘ １０
−’ｍｏｌ！／ｍｉｎ、供給し、ＴＭＧ供給量を７ Ｘ
１ （）−６ｍｏ １／ｍｉｎ、５ｉＨ４供給量を５
Ｘ １０’ｍｏ Ｉ！ ／ｍｉｎ、に変え、ｎ型ＡＲＧ
ａＡｓ５を形成する。次にＴＭＡをＩ Ｘ １０−６ｍ
ｏ Ｉ ／ｍｉｎ、、ＴＭＧを９ＸＩＯ−’ｍｏＡ’／
ｍ ｉ ｎ 、に変化させ、ＳｉＨ４、ＴＭＡの供給を
止め、ＧａＡｓ ６を形成する。次に、ＴＭＡを３×ｌ
Ｏ−６ｍｏｌ／ｍｉｎ、、ＴＭＧを７ｘ １０＝ｍｏ
Ｉ！／ｍｉｎ、に変え、ＤＥＺｎを５ Ｘ １０−’ｍ
ｏ １２ ／ ｍｉｎ、供給し、ｐ型ＡＩ！ＧａＡｓ
７を形成する。次に、ＴＭＡの供給を止め、ＴＭＧを７
Ｘ１０−６ｍｏ ｊ！ ／ｍｉｎ、、ＤＥＺｎを２ Ｘ
１０−’ｍｏｆ／ｍｉｎ、に変え、ｎ型ＧａＡｓ Ｂ
を形成した。Next, as shown in FIG. 4(f), the supply of HCI gas was stopped, and TMA (1-lymphylgallium) was added to 3×10
-'mol! /min, and the TMG supply amount is 7
1 ()-6mo 1/min, 5iH4 supply amount 5
X 10'mo I! /min, change to n-type ARG
Form aAs5. Then TMA I x 10-6m
o I /min,, TMG is 9XIO-'moA'/
m i n , the supply of SiH4 and TMA is stopped, and GaAs 6 is formed. Next, add 3×l TMA
O-6mol/min, TMG 7x 10=mo
I! /min, and DEZn to 5 x 10-'m.
o 12/min, supply, p-type AI! GaAs
form 7. Next, stop the TMA supply and increase the TMG to 7
X10-6mo j! /min,, DEZn 2 X
10-'mof/min, n-type GaAs B
was formed.
第４図（ｇ）に示すように成長表面にＡ ｕ ／ Ｚ
ｎ ／Ａｕ電極１３を、基板裏面にＡｕＧｅ電極１４を
抵抗加熱蒸着した。As shown in Figure 4(g), A u / Z is formed on the growth surface.
An n /Au electrode 13 and an AuGe electrode 14 were deposited on the back surface of the substrate by resistance heating vapor deposition.
以上のように１回の成長で製作された埋め込み型発光素
子の基本特性を測定した。酸化タンタルを形成した部分
からの発光が観測され、他の部分での耐圧が５ｖ有り、
電流狭窄層が形成されていた。The basic characteristics of the embedded light emitting device fabricated in one growth process as described above were measured. Luminescence was observed from the part where tantalum oxide was formed, and the withstand voltage in other parts was 5V.
A current confinement layer was formed.
以上説明したように、選択成長を行う際、マスクとして
酸化タンタルを用い、原料ガスとともにＨＣｆガスを供
給することにより、高選択性を得ることができるととも
に、酸化タンタルの膜厚を制御することにより選択成長
、全面成長を１つの成長プロセスの中で行うことができ
る。As explained above, when performing selective growth, high selectivity can be obtained by using tantalum oxide as a mask and supplying HCf gas together with the source gas, and by controlling the film thickness of tantalum oxide. Selective growth and full-scale growth can be performed in one growth process.
第１図は本発明による結晶成長法説明図。
第２図は酸化タンタル作成条件による酸化タンタル上に
形成されたＧａＡｓ単結晶核密度の変化を示す図。
第３図は本発明による結晶成長法実施例１を説明するた
めの図。
第４図は本発明による結晶成長法実施例２を示すための
図。
第５図はＨＣＡ供給量による酸化タンタル上に形成され
たＧａＡｓ単結晶核密度の変化を示すための図。
１・・・酸化タンタル
２・・・ＧａＡｓ （ガリウムヒ素）、ＩｎＰ （イン
ジウムリン）、Ｓｉ等の単結晶基板
３・・・Ｖ族原料、■族原料、ＭＣＩ！ガス４・・・ｎ
型ＧａＡｓ （ガリウムヒ素）基板５・・・ｎ型ＧａＡ
Ｉ Ａｓ （ガリウムアルミニウムヒ素）膜
６・・・ＧａＡｓ （ガリウムヒ素）膜７・・・ｐ型Ｇ
ａＡ Ｉ！ Ａｓ （ガリウムアルミニウムヒ素）膜
８・・・ｎ型ＧａＡｓ （ガリウムヒ素）膜９・・・ｎ
型ＧａＡｓ （ガリウムヒ素）膜１０・・・エツチング
された酸化タンタル形成部１１・・・ｎ型ＧａＡｓ （
ガリウムヒ素）膜１２・・・ｎ型ＧａＡｓ （ガリウム
ヒ素）膜１３−−・Ａ ｕ ／ Ｚ ｎ ／ Ａ ｕ電
極１４−−・Ａ ｕ Ｇ ｅ電極
１５・・・レジスト
−Ｖ乙りンタル乍釈謬書千１ごよる面晩イ乙タンタル工
１てｈｎ＝ｙＮｒｃ Ｄａ４ ＊＃；ｊ−不阪ｄｌＫｎ
変イ乙八・７７へ′ｌシント ／Ｘｌ０−’Ｔｔｒｎｎ
６ソ併胎量 （ｃｃ／ｍｉｎン
第 ３ 図
（（２＞
（ｂ）
（Ｃ）
（ｄ）
（ε）
（’ｆ）FIG. 1 is an explanatory diagram of the crystal growth method according to the present invention. FIG. 2 is a diagram showing changes in the density of GaAs single crystal nuclei formed on tantalum oxide depending on tantalum oxide production conditions. FIG. 3 is a diagram for explaining Example 1 of the crystal growth method according to the present invention. FIG. 4 is a diagram showing Example 2 of the crystal growth method according to the present invention. FIG. 5 is a diagram showing changes in the density of GaAs single crystal nuclei formed on tantalum oxide depending on the amount of HCA supplied. 1... Tantalum oxide 2... Single crystal substrate of GaAs (gallium arsenide), InP (indium phosphide), Si, etc. 3... Group V raw material, Group ■ raw material, MCI! Gas 4...n
Type GaAs (gallium arsenide) substrate 5... n-type GaA
I As (gallium aluminum arsenide) film 6...GaAs (gallium arsenide) film 7...p-type G
aAI! As (gallium aluminum arsenide) film 8... n-type GaAs (gallium arsenide) film 9... n
Type GaAs (gallium arsenide) film 10...etched tantalum oxide forming portion 11...n type GaAs (
Gallium arsenide) film 12...N-type GaAs (gallium arsenide) film 13--Au/Zn/Au electrode 14--AuGe electrode 15...Resist-V 100000001
Weird Otohachi 77 to 'l sint /Xl0-'Ttrnn
Figure 3 ((2> (b) (C) (d) (ε) ('f)
Claims (3)
単結晶あるいは多結晶を形成しない非形成面として酸化
タンタルを用い、塩素を含む原料ガスを供給することを
特徴とする選択結晶成長方法。(1) In a selective crystal growth method using vapor phase growth,
A selective crystal growth method characterized by using tantalum oxide as a non-forming surface that does not form single crystals or polycrystals, and supplying a raw material gas containing chlorine.
１記載の選択結晶成長方法。(2) The selective crystal growth method according to claim 1, wherein the crystal forming raw material gas and hydrogen chloride are supplied.
項１記載の選択結晶成長方法。(3) The selective crystal growth method according to claim 1, wherein the single crystal is a III-V group compound semiconductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30497390A JPH04175293A (en) | 1990-11-09 | 1990-11-09 | Method for selective crystal growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30497390A JPH04175293A (en) | 1990-11-09 | 1990-11-09 | Method for selective crystal growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04175293A true JPH04175293A (en) | 1992-06-23 |
Family
ID=17939543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30497390A Pending JPH04175293A (en) | 1990-11-09 | 1990-11-09 | Method for selective crystal growth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04175293A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982435B2 (en) * | 1999-03-31 | 2006-01-03 | Toyoda Gosei Co., Ltd. | Group III nitride compound semiconductor device and method for producing the same |
-
1990
- 1990-11-09 JP JP30497390A patent/JPH04175293A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982435B2 (en) * | 1999-03-31 | 2006-01-03 | Toyoda Gosei Co., Ltd. | Group III nitride compound semiconductor device and method for producing the same |
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