JPH04182385A - Growing method for crystal - Google Patents
Growing method for crystalInfo
- Publication number
- JPH04182385A JPH04182385A JP30790990A JP30790990A JPH04182385A JP H04182385 A JPH04182385 A JP H04182385A JP 30790990 A JP30790990 A JP 30790990A JP 30790990 A JP30790990 A JP 30790990A JP H04182385 A JPH04182385 A JP H04182385A
- Authority
- JP
- Japan
- Prior art keywords
- nucleation
- crystal
- tantalum oxide
- raw material
- single crystal
- 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 55
- 238000000034 method Methods 0.000 title abstract description 27
- 230000006911 nucleation Effects 0.000 claims abstract description 42
- 238000010899 nucleation Methods 0.000 claims abstract description 42
- 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 32
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000002109 crystal growth method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002159 abnormal effect Effects 0.000 abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007740 vapor deposition Methods 0.000 abstract description 5
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000070 arsenic hydride Inorganic materials 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 abstract 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 102000016942 Elastin Human genes 0.000 description 2
- 108010014258 Elastin Proteins 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229920002549 elastin Polymers 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 2
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KOWWOODYPWDWOJ-LVBPXUMQSA-N elatine Chemical compound C([C@]12CN(C3[C@@]45OCO[C@]44[C@H]6[C@@H](OC)[C@@H]([C@H](C4)OC)C[C@H]6[C@@]3([C@@H]1[C@@H]5OC)[C@@H](OC)CC2)CC)OC(=O)C1=CC=CC=C1N1C(=O)CC(C)C1=O KOWWOODYPWDWOJ-LVBPXUMQSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 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ｍ−ｖ族化合物半導体の結晶成長法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for growing crystals of m-v group compound semiconductors.
［従来の技術］
従来、Ｇ ａ Ａ ｓ単結晶を形成する場合、Ｇａ Ａ
ｓ単結晶基板上にエピタキシャル成長させることにより
形成している。しかし、このような単結晶基板上てのエ
ピタキシャル成長ては、単結晶基板の材料による制約か
あり、大面積化、３次元集積化か不可能となっている。[Prior Art] Conventionally, when forming a GaAs single crystal, GaA
It is formed by epitaxial growth on a single crystal substrate. However, such epitaxial growth on a single-crystal substrate is limited by the material of the single-crystal substrate, making it impossible to increase the area or achieve three-dimensional integration.
これに対し、光並列処理などに用いられる大面積アレー
や３次元光集積回路に対する要求か強まり、単結晶の非
晶質基板上への成長技術か望まれている。この非晶質基
板上へ単結晶を成長する技術として選択核形成法（特開
昭６３−２３７５１７号）かある。On the other hand, there is an increasing demand for large area arrays and three-dimensional optical integrated circuits used in optical parallel processing, etc., and a growth technique for single crystals on amorphous substrates is desired. As a technique for growing a single crystal on this amorphous substrate, there is a selective nucleation method (Japanese Patent Laid-Open No. 63-237517).
選択核形成法とは、非晶質あるいは多結晶である核形成
密度の小さい非核形成面と、単一核のみより結晶成長す
るに十分小さい面積を有し、該非核形成面の核形成密度
より大きい核形成密度を有する非晶質あるいは多結晶で
ある核形成面とが隣接して配された自由表面を有する基
板に、結晶形成処理を施して該単一核より単結晶を成長
させるものである。The selective nucleation method consists of a non-nucleation surface that is amorphous or polycrystalline and has a low nucleation density, and an area that is sufficiently small to allow crystal growth from a single nucleus, and a surface that is smaller than the nucleation density of the non-nucleation surface. A substrate having a free surface adjacent to an amorphous or polycrystalline nucleation surface having a high nucleation density is subjected to crystal formation treatment to grow a single crystal from the single nucleus. be.
」−記選択核形成法ては、非核形成面として酸化ケイ素
、窒化けい素か用いられてし入る。The selective nucleation method uses silicon oxide or silicon nitride as the non-nucleation surface.
［発明か解決しようとしている課題］
しかしながら、上記従来例ては非核形成面の面積か大き
くなると酸化けい素、窒化はし＼素等の上にＧａＡｓ単
結晶核あるいは多結晶等の異常核か形成されてしまうこ
とがあった。[Problem to be solved by the invention] However, in the above conventional example, when the area of the non-nucleation surface becomes large, GaAs single crystal nuclei or abnormal nuclei such as polycrystals are formed on silicon oxide, nitride, etc. There have been times when I have been
［課題を解決するための手段］
本発明の結晶成長法は、非晶質あるいは多結晶である酸
化タンタルを非核形成面とし、該非核形成面と、単一核
のみより結晶成長するに十分小さい面積を有し、単一核
より結晶成長するに十分な大きさの核形成密度を有する
非晶質あるいは多結晶である核形成面とが隣接して配さ
れた自由表面を有する基板に、結晶形成処理を施す際、
塩素を含む原料ガスを供給することを特徴とする。[Means for Solving the Problems] The crystal growth method of the present invention uses amorphous or polycrystalline tantalum oxide as a non-nucleation surface, and combines the non-nucleation surface with a material that is small enough to allow crystal growth from a single nucleus alone. A crystal is formed on a substrate having a free surface adjacent to an amorphous or polycrystalline nucleation surface having a large area and a nucleation density large enough for crystal growth from a single nucleus. When performing the forming process,
It is characterized by supplying a raw material gas containing chlorine.
本発明は、選択核形成法を用いて非単結晶」−に結晶形
成処理を施す際に、塩素を含む原料ガスを供給し、非核
形成面として、酸化けい素や窒化けい素に比へ、塩素を
含む原料カスに対して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。In the present invention, when a non-single crystal is subjected to a crystal formation process using a selective nucleation method, a source gas containing chlorine is supplied, and as a non-nucleation surface, silicon oxide or silicon nitride is used as a non-nucleation surface. This method uses tantalum oxide, which can be etched more quickly against raw material residue containing chlorine.
［作用］
非核形成面とする酸化タンタルをエツチングする塩素を
含む原料カスを供給することにより、非核形成面上に単
結晶あるいは多結晶か生ずる異常核発生を抑制し、選択
性を向上てきる。[Operation] By supplying raw material scum containing chlorine for etching tantalum oxide, which is used as a non-nucleation surface, abnormal nucleation of single crystals or polycrystals on the non-nucleation surface can be suppressed and selectivity can be improved.
［実施態様例］ 本発明の実施態様例を示す。[Example of implementation] An example embodiment of the present invention is shown.
まず第１図に示すようにＳｉ、 Ｇａ Ａｓ ｌｎＰ
等の単結晶基板あるいはＳｉｏ。、ＡｕＪ３等のセラミ
ック基板あるいはＭｏ、Ｗ等の高融点金属基板を用い、
これらの耐熱性基板、表面に非核形成面部分に酸化タン
タル、を形成し、核形成面部分に酸化アルミニウム、窒
化アルミニウム、酸化チタン、窒化チタン等の塩化水素
に対して比較的エラチンクレートか遅く核形成密度が大
きい非単結晶２か露出した面を形成する。あるいは、酸
化アルミニウム、窒化アルミニウム等の核形成密度か大
きい非晶質あるいは多結晶質の非単結晶２を形成し、非
核形成面部分に酸化タンタル１が露出した面を形成して
も構わない。First, as shown in Figure 1, Si, GaAs lnP
A single crystal substrate such as Sio. , using a ceramic substrate such as AuJ3 or a high melting point metal substrate such as Mo or W,
These heat-resistant substrates have tantalum oxide formed on the non-nucleation surface, and aluminum oxide, aluminum nitride, titanium oxide, titanium nitride, etc. on the nucleation surface, which are relatively slow to elastinate against hydrogen chloride. A non-single crystal 2 with a high nucleation density forms an exposed surface. Alternatively, an amorphous or polycrystalline non-single crystal 2 having a high nucleation density such as aluminum oxide or aluminum nitride may be formed, and a surface where tantalum oxide 1 is exposed may be formed on the non-nucleation surface portion.
酸化タンタルの形成法としては、ＥＢ（電子線）蒸着法
、スパッタ法を等用いる。As a method for forming tantalum oxide, an EB (electron beam) evaporation method, a sputtering method, etc. are used.
つぎに、ＭＯＣＶＤ法（有機金属気相成長法）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ＡｓＨ。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, AsH was used as the group V raw material.
ＴＢＡｓ （ターシャルブチルアルシン）、ＴＭＡｓ
（トリメチルアルシン） 、 ＰＨ３，ＴＢＰ（タ
ーシャルブチルホスフィン）等を用いる。TBAs (tertiary butylarsine), TMAs
(trimethylarsine), PH3, TBP (tertiary butylphosphine), etc. are used.
また■族原料としては、ＴＭＧ （１−リメチルガリウ
ム）、ＴＥＧ （トリエチルガリウム）、ＴＭＡ （１
−リメチルアルミニウム）、ＴＥＡ （）−リエチルア
ルミニウム）、ＴＭＩｎ（トリメチルインジウム）、Ｔ
ＥＩｎ （トリエチルインジウム）等の原料か用いら
れる。これらの原料と同時にＭＣＩカス３を供給し、選
択核形成法を行う。Group III raw materials include TMG (1-limethyl gallium), TEG (triethyl gallium), and TMA (1-limethyl gallium).
-limethylaluminum), TEA ()-liethylaluminum), TMIn (trimethylindium), T
Raw materials such as EIn (triethyl indium) are used. MCI dregs 3 is supplied simultaneously with these raw materials, and a selective nucleation method is performed.
ＭＯＣＶＤ法を用いてＧａ Ａｓの選択核形成法を行う
場合、以下のような条件て行う。成長温度は一般には５
００〜８００°Ｃ５望ましくは５７０〜７６０°Ｃ１最
適には６００〜７００°Ｃて行い、圧力は一般には７６
０Ｔｏｒｒ以下、望ましくはｌ００Ｔｏｒｒ以下、最適
には２０ Ｔｏｒｒ以下て行う。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
ｌＯ〜２００最適には３０〜１５０て行い、原料ととも
に供給するＨＣＴの供給モル量の全供給カスに占める割
合は一般には１〜１．０００ｐｐｍ 、望ましくは１〜
５００ｐｐｍ、最適には５〜１１００ｐｐとする。When selective nucleation of GaAs is performed using the MOCVD method, it is performed under the following conditions. The growth temperature is generally 5
00-800°C5 Desirably 570-760°C1 Optimal temperature is 600-700°C, and the pressure is generally 76°C.
It is carried out at a pressure of 0 Torr or less, preferably 100 Torr or less, most preferably 20 Torr or less. Also, V group raw material supply amount/
The ratio of the amount of group raw materials supplied is generally 5 to 300, preferably 10 to 200, and optimally 30 to 150. .000ppm, preferably 1~
500 ppm, optimally 5 to 1100 ppm.
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、ＭＯＣＶＤ
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−Ｌに形成される単結晶核の数は
異なることが分かる。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か異なること
を示していると考えられる。第２図か極小値を持ってい
ることは、酸素の組成比か大きい場合には酸化タンタル
のエラチンクレートか小さくなりＧａ Ａｓの形成を抑
制することが出来なくなるためＧａ Ａｓ単結晶核か増
加し、酸素の組成比か小さい場合には酸化タンタルの表
面モホロジーか悪化するためにＧａ Ａｓ単結晶核か増
加すると考えられる。ここて、ＭＯＣＶＤ法を用いた結
晶形成処理の条件は、まず基板温度７６０°Ｃ１圧力］
００ＴｏｒｒてＡ ｓ Ｈ：＋を６ Ｘ １０−４ｍｏ
ｌ／ｍｉｎ 、水素を１０文／ｍｉｎ、供給し、２０分
間、表面処理を行う。In addition, when forming tantalum oxide using the EB evaporation method, samples were created with varying amounts of oxygen supplied, and then MOCVD
A crystal formation process was performed using the method, and the density of single crystal nuclei formed on a 5 cm square tantalum oxide was measured. The results are shown in FIG. From this, it can be seen that the number of single crystal nuclei formed in tantalum oxide-L varies depending on the production conditions of tantalum oxide. This is considered to indicate that the number of single crystal nuclei formed on tantalum oxide differs depending on the composition of tantalum oxide. The fact that it has a minimum value in Figure 2 means that when the oxygen composition ratio is large, the elastin crater of tantalum oxide becomes small and the formation of GaAs cannot be suppressed, so the number of GaAs single crystal nuclei increases. However, if the oxygen composition ratio is small, the surface morphology of tantalum oxide deteriorates, and it is thought that the number of GaAs single crystal nuclei increases. Here, the conditions for the crystal formation treatment using the MOCVD method are: first, the substrate temperature is 760°C and the pressure is
00 Torr A s H: +6 x 10-4mo
1/min, hydrogen was supplied at 10 m/min, and surface treatment was performed for 20 minutes.
その後基板温度７８０°Ｃ１圧力１０ Ｔｏｒｒで原料
ガスとしてＡｓ Ｈ３を４ Ｘ １０ ”−４ｍｏｌ／
ｍｉｎ、ＴＭＧをＩ Ｘ １０−５ｍｏｌ／ｍｉｎ 、
水素を１０文／ｍｉｎ、ＨＣｌガスを２ Ｘ １０−’
ｍｏｌ／ｍｉｎ 、を２０分供給した。After that, As H3 was added as a raw material gas at a substrate temperature of 780°C and a pressure of 10 Torr at a concentration of 4×10”-4mol/
min, TMG at I×10−5 mol/min,
Hydrogen at 10 sentences/min, HCl gas at 2 x 10-'
mol/min was supplied for 20 minutes.
また、ＨＣｕ供給量を変化させ、５ｃｍ角の酸化タンタ
ルＩ−に形成されるＧ ａ Ａ ｓ ｒｌｉ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５ｃｍ角の酸化けい素−１−に形成された
Ｇ ａ Ａ ｓ 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ｂ
っでいることが分かる。これはＨＣ文供給量か少ない場
合には酸化タンタルのエラチンクレートか小さくなりＧ
ａＡｓの形成を抑制することが出来なくなるためＧ ａ
Ａ ｓ単結晶核が増加し、ＨＣＩ供給量か多い場合に
はエラチンクレートか大きすきるため、酸化タンタルの
表面モホロジーか悪化するためにＧａＡｓ単結晶核か増
加すると考えられる。ここて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１０ｃ ｃ
／ ｍ ｉ ｎ、である。また結晶形成処理はＭＯＣ
ＶＤ法を用いて、まず基板温度７６０°Ｃ圧力］００Ｔ
ｏｒｒてＡ ｓ Ｈ３を６ Ｘ １０−’ｍｏｌ／＋＋
＋ｉｎ水素を１０文／ｍｉｎ、供給し、２０分間、表面
処理を行う。その後基板温度７８０°Ｃ１圧力１０ Ｔ
ｏｒｒて原料ガスとしてＡｓＨ３を４×１０ ”−’ｍ
ｏｌ／ｍｉｎ 、 Ｔ Ｍ Ｇをｌ Ｘ １０−５ｍｏ
ｌ／ｍｉｎ水素を１０ｆ／ｍｉｎ 、ＨＣＩガスを２Ｘ
１０−５ｍｏｌ／ｍｉｎを２０分供給した。In addition, the HCu supply amount was changed and changes in the density of Ga As rli crystal nuclei formed in a 5 cm square tantalum oxide I- were measured. For comparison, changes in the number of GaAs single crystal nuclei formed on a 5 cm square silicon oxide-1- obtained by thermal oxidation treatment of a Si substrate were investigated by performing crystal formation treatment at the same time as tantalum oxide. . The results are shown in FIG. Tantalum oxide has a minimum value b for HCI supply amount.
I can see that there is. This means that if the HC supply is low, the tantalum oxide elatin crate will become smaller.
Since the formation of aAs cannot be suppressed, Ga
It is thought that the number of GaAs single crystal nuclei increases because the number of As single crystal nuclei increases, and when the amount of HCI supplied is large, the size of the elastin crate becomes large, and the surface morphology of tantalum oxide deteriorates. The tantalum oxide used here is EB
It is created by vapor deposition, and the amount of oxygen supplied at this time is 10 c c
/min. Also, the crystal formation process is MOC
Using the VD method, first the substrate temperature is 760°C and the pressure is 00T.
Orr A s H3 6 X 10-'mol/++
+in hydrogen was supplied at 10 m/min, and surface treatment was performed for 20 minutes. Then substrate temperature 780°C1 pressure 10T
AsH3 was used as the raw material gas at 4×10''-'m
ol/min, TMG to l x 10-5mo
l/min hydrogen 10f/min, HCI gas 2X
10 −5 mol/min was supplied for 20 minutes.
［実施例］ 本発明の実施例を示す。[Example] An example of the present invention is shown.
まず第３図（ａ）に示すように、Ｓｉ基板４上に酸化ア
ルミニウム５を２０００Ａ 、酸化タンタル１を５０Ｏ
Ａ連続的にＥＢ蒸着により形成した。ここてＥＢ蒸着の
条件としては、ハッククランドを１０”−６７ｏｒｒま
て真空にし、次に０２を１０ ｃｃ／ｍｉｎ供給し蒸着
した。First, as shown in FIG. 3(a), aluminum oxide 5 was placed on a Si substrate 4 at 2000A, and tantalum oxide 1 was placed at 500A on a Si substrate 4.
A was formed by continuous EB deposition. The conditions for EB deposition were as follows: Hackland was evacuated to 10"-67 orr, and then 02 was supplied at 10 cc/min for deposition.
続いて、第３図（ｂ）に示すようにホトリソクラフイに
より２００ｐｍピッチて２ＪＬｍφのドツトを抜いたパ
ターンを形成した。Subsequently, as shown in FIG. 3(b), a pattern in which dots of 2JLmφ were punched out at a pitch of 200pm was formed by photolithography.
続いて第３図（ｃ）に示すようにＩＢＥにより２上ｍφ
ドツト部以外の酸化タンタルを残し、１〜ツｌ一部表面
に酸化アルミニウムを露出させた。ここてＩＢＥの条件
は、ＣＦ 、、を２０ＣＣ／ｌ１１１ｎＯ２を２ ｃｃ
／ｍｉｎ供給し、圧力１０Ｐａパワー１００ＷてｌＯ分
間エッチンクした。Then, as shown in Fig. 3(c), 2 upper mφ was obtained by IBE.
Tantalum oxide was left in areas other than the dots, and aluminum oxide was exposed on a portion of the surface. Here, the IBE conditions are CF, 20CC/l111nO2 2cc
/min, and etching was performed for 10 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、レシス１〜１５を取
り去り、表面の清純化を行いＭＯＣＶＤ法を用いて基板
温度７６０℃、圧力］ｆｌＯＴｏｒｒてＡｓＨ３を６
Ｘ １０−’Ｉｎｏｌ／ｌｌ１ｉｎ 、水素を１０ｆｌ
／ｍｉｎ供給し、２０分間、表面処理を行った第３図（
ｅ）。その後基板温度７６０°Ｃ１圧力２０ Ｔｏｒｒ
て原料カスとしてＡ ｓ” Ｈ：＋を４×１０−’ｍｏ
ｌ／ｍｉｎ 、 ＴＭＧをＩ Ｘ １０−５ｍｏｌ／ｍ
ｉｎ水素を１０ ｆＬ ／ｍｉｎ、ＨＣＩカスを２×１
０ ”−’ｍｏｌ／ｌｌ１ｉｎ 、供給してＧａＡｓ単
結晶単結晶形９する（１時間）。As shown in FIG. 3(d), Resis 1 to 15 were then removed, the surface was purified, and AsH3 was removed using the MOCVD method at a substrate temperature of 760°C and a pressure of 60°C.
X 10-'Inol/ll1in, 10 fl of hydrogen
/min and surface treatment was performed for 20 minutes.
e). After that, the substrate temperature was 760°C and the pressure was 20 Torr.
A s"H:+ is 4×10-'mo as raw material waste.
l/min, TMG I x 10-5 mol/m
in hydrogen at 10 fL/min, HCI sludge at 2×1
0''-'mol/ll1in to form a GaAs single crystal (1 hour).
非核形成面としてＳｉｏ２を用いて、同一条件て結晶形
成処理をした場合、Ｓｉｏ□上にＧ ａ Ａ ｓ単結晶
核は４７個／ｃｍ２てあったのに対して、酸化タンタル
上に形成された
ＧａＡｓ単結晶核は２６個／ｃ＋＋＋２てあり、選択性
か向上したことが示された。When crystal formation was performed under the same conditions using Sio2 as a non-nucleation surface, there were 47 GaAs single crystal nuclei/cm2 on Sio2, whereas 47 GaAs single crystal nuclei were formed on tantalum oxide. The number of GaAs single crystal nuclei was 26/c+++2, 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８１基板４上に酸化タンタル
１を２０００Ａ 、窒化アルミニウム６を５００Ｘ、Ｅ
Ｂ蒸着により形成した。ここでＥＢ蒸着の条件としては
、ハッククランドを１Ｏ−６Ｔｏｒｒまて真空にし、次
に０２を１０ ｃｃ／ｍｉｎ供給し、蒸着した。As shown in Fig. 4(a), tantalum oxide 1 was applied at 2000A on 81 substrate 4, aluminum nitride 6 was applied at 500X, E
It was formed by B vapor deposition. Here, the conditions for EB vapor deposition were as follows: Huckland was evacuated to 10-6 Torr, and then 02 was supplied at 10 cc/min for vapor deposition.
続いて第４図（ｂ）に示すようにホトリソタラフイによ
り５００ｐｍピッチて］、、２７ｐｍφのドツトを残し
たパターンを形成し、ＩＢＨにより１．２ ｐ−ｍφの
ドツト部以外の窒化アルミニウムを取り去り、酸化タン
タルを表面に露出させた（第４図（Ｃ））。ここてＩＢ
Ｅの条件はＣＧ１２Ｆ２を１０ ｃｃ／ｍｉｎ、 Ａ
ｒを２ ｃｃ／ｍｉｎ供給し、圧力４Ｐａ、パワー１３
０Ｗて１０分間エツチングした。Next, as shown in FIG. 4(b), a pattern was formed with dots of 27 pmφ at a pitch of 500 pm using photolithography, and aluminum nitride other than the dots of 1.2 pmφ was removed by IBH, and then oxidized. Tantalum was exposed on the surface (Figure 4(C)). Kokote IB
Conditions for E are CG12F2 at 10 cc/min, A
Supply r at 2 cc/min, pressure 4 Pa, power 13
Etching was performed for 10 minutes at 0W.
その後、レジスト１５を取り去り、表面の清純化を行っ
た（第４図（ｄ））。Thereafter, the resist 15 was removed and the surface was purified (FIG. 4(d)).
Ｍ０ＣＶＤ法を用いて基板温度８６０°Ｃ１圧力］００
ＴｏｒｒてＡ ｓ Ｈｚを４ ｘ ｌ Ｏ−’ｍｏｌ／
ｍｉｎ、水素を１０文／ｍｉｎ、供給し、２０分間、表
面処理を行った（第４図（ｅ））。その後基板温度７７
５℃、圧力２０ Ｔｏｒｒて原料ガスとしてＡｓＨ３を
４ Ｘ １０−’ｍｏｌ／ｍｉｎ 、 Ｔ Ｍ Ｇを１
×１０−５ｍｏｌ／ｍｉｎ 、水素を１０９．／ ｍｉ
ｎ、ＨＣＩガスを２ ｘ １０−”ｍｏｌ／Ｉｌ］ｉｎ
、供給してＧａＡｓ単結晶核９を形成するく１時間）
。Using M0CVD method, substrate temperature 860°C1 pressure]00
Torr and A s Hz 4 x l O-'mol/
Hydrogen was supplied at a rate of 10 m/min and surface treatment was performed for 20 minutes (FIG. 4(e)). Then the substrate temperature is 77
At 5°C and a pressure of 20 Torr, AsH3 was used as the raw material gas at 4 x 10-'mol/min, and TMG was used at 1
×10-5 mol/min, hydrogen at 109. / mi
n, HCI gas at 2 x 10-”mol/Il]in
, for 1 hour to form GaAs single crystal nuclei 9)
.
非核形成面として、Ｓ ｉ Ｏ２を用いて、同一条件て
結晶形成処理を行った場合、Ｓ １０２１に発生した異
常核密度は６５個／Ｃｍ２てあったのに対して、酸化タ
ンタル上の異常核密度は３０個／ｃｍ２てあり、異常核
の発生か抑えられた。When crystal formation was performed under the same conditions using SiO2 as a non-nucleation surface, the density of abnormal nuclei generated on S1021 was 65/Cm2, whereas the density of abnormal nuclei on tantalum oxide was 65/Cm2. The density was 30/cm2, and the occurrence of abnormal nuclei was suppressed.
［発明の効果］
以上説明したように、選択核形成法を行う際、非核形成
面として酸化タンタルを用い、原料ガスとともにＨＣ１
ｊガスを供給することにより、異常核発生を抑え選択性
を向」ニさせることがてきる。[Effect of the invention] As explained above, when performing the selective nucleation method, tantalum oxide is used as a non-nucleation surface, and HC1 is used together with the raw material gas.
By supplying J gas, abnormal nucleation can be suppressed and selectivity can be improved.
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単結晶単結晶変数を示す図。
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を説明するた
めの図。
第５図はＨＣＩ供給量による酸化タンタル上に形成され
たＧａＡｓ単結晶単結晶変数を示す図。
１・・・酸化タンタル
２・・・核形成面
３・・・Ｖ族原料、■族原料、ＨＣ又ガス４・・・Ｓｉ
基板
５・・・酸化アルミニウム
６・・・窒化アルミニウム
９・・・ＧａＡｓ単結晶核
１５・・・レシスト
＼
へ ＼
′−稿 ト 賜FIG. 1 is an explanatory diagram of the crystal growth method according to the present invention. FIG. 2 is a diagram showing single crystal parameters of GaAs single crystal formed on tantalum oxide under 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 for explaining Example 2 of the crystal growth method according to the present invention. FIG. 5 is a diagram showing the single crystal parameters of GaAs single crystal formed on tantalum oxide depending on the amount of HCI supplied. 1... Tantalum oxide 2... Nucleation surface 3... Group V raw material, Group II raw material, HC or gas 4... Si
Substrate 5...Aluminum oxide 6...Aluminum nitride 9...GaAs single crystal nucleus 15...Resist
Claims (3)
形成面とし、該非核形成面と、単一核のみより結晶成長
するに十分小さい面積を有し、単一核より結晶成長する
に十分な大きさの核形成密度を有する非晶質あるいは多
結晶である核形成面とが隣接して配された自由表面を有
する基板に、結晶形成処理を施す際、塩素を含む原料ガ
スを供給することを特徴とする結晶成長法。(1) Amorphous or polycrystalline tantalum oxide is used as a non-nucleation surface, and the non-nucleation surface and the area are sufficiently small to allow crystal growth from a single nucleus, and are sufficient to allow crystal growth from a single nucleus. A source gas containing chlorine is supplied when performing crystal formation treatment on a substrate having a free surface adjacent to an amorphous or polycrystalline nucleation surface having a nucleation density of a certain size. A crystal growth method characterized by:
１記載の結晶成長法。(2) The crystal growth method according to claim 1, wherein the crystal forming raw material gas and hydrogen chloride are supplied.
項１記載の結晶成長法。(3) The 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 |
|---|---|---|---|
| JP30790990A JPH04182385A (en) | 1990-11-13 | 1990-11-13 | Growing method for crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30790990A JPH04182385A (en) | 1990-11-13 | 1990-11-13 | Growing method for crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04182385A true JPH04182385A (en) | 1992-06-29 |
Family
ID=17974633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30790990A Pending JPH04182385A (en) | 1990-11-13 | 1990-11-13 | Growing method for crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04182385A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030012797A (en) * | 2001-08-01 | 2003-02-12 | 후지쯔 가부시끼가이샤 | Polycrystalline structure film and method of making same |
| US7285312B2 (en) * | 2004-01-16 | 2007-10-23 | Honeywell International, Inc. | Atomic layer deposition for turbine components |
-
1990
- 1990-11-13 JP JP30790990A patent/JPH04182385A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030012797A (en) * | 2001-08-01 | 2003-02-12 | 후지쯔 가부시끼가이샤 | Polycrystalline structure film and method of making same |
| US7285312B2 (en) * | 2004-01-16 | 2007-10-23 | Honeywell International, Inc. | Atomic layer deposition for turbine components |
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