JPH0740560B2 - Method for manufacturing compound semiconductor film - Google Patents
Method for manufacturing compound semiconductor filmInfo
- Publication number
- JPH0740560B2 JPH0740560B2 JP27169686A JP27169686A JPH0740560B2 JP H0740560 B2 JPH0740560 B2 JP H0740560B2 JP 27169686 A JP27169686 A JP 27169686A JP 27169686 A JP27169686 A JP 27169686A JP H0740560 B2 JPH0740560 B2 JP H0740560B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- semiconductor film
- compound semiconductor
- gas
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims description 56
- 239000004065 semiconductor Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 13
- 239000007789 gas Substances 0.000 claims description 26
- 239000012535 impurity Substances 0.000 claims description 20
- 150000001350 alkyl halides Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 3
- 125000002521 alkyl halide group Chemical group 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- -1 HCl gas is used Chemical class 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 7
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 3
- 229910000058 selane Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910004262 HgTe Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910007709 ZnTe Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Led Devices (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は，元素の周期表第IIb族元素および第VIb族元素
よりなる化合物半導体膜の製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing a compound semiconductor film comprising an element of Group IIb and an element of Group VIb of the periodic table of elements.
近年，青色発光材料として注目されているZnS,ZnSeなど
の化合物半導体膜を製造する方法として，有機金属化学
気相成長法（MOCVD法……Metal Organic Chemical Vapo
r Deposition法）と呼ばれている方法が多く採用される
ようになった。このMOCVD法では，例えばジメチル亜鉛
〔(CH3)2Zn〕などの元素の周期表第IIb族元素を含む有
機金属化合物を気相熱分解し，セレン化水素(H2Se)など
の第VIb族元素を含む化合物と反応させることによって,
ZnSeなどの第IIb族−第VIb族化合物半導体膜を基板上に
成長させていた。そして,n型伝導性を有する化合物半導
体膜を得ることを目的とした従来の方法では，原料ガス
中にAl,Geなどの第IIIb族元素を含む有機金属化合物を
添加しているが，この方法では不純物として第IIIb族元
素の添加による化合物半導体膜の劣化が起り易く，例え
ば1017個／cm3以下のキャリア濃度でも青色発光材料と
して使用できない程度にまで化合物半導体膜の劣化が生
じるという欠点があった。In recent years, as a method for producing a compound semiconductor film such as ZnS and ZnSe, which has been attracting attention as a blue light emitting material, a metal organic chemical vapor deposition method (MOCVD method ... Metal Organic Chemical Vapo
r Deposition method) has come to be adopted a lot of methods. In this MOCVD method, for example, an organometallic compound containing a Group IIb element of the periodic table of an element such as dimethyl zinc [(CH 3 ) 2 Zn] is vapor-phase thermally decomposed to produce a VIb such as hydrogen selenide (H 2 Se). By reacting with a compound containing a group element,
A Group IIb-Group VIb compound semiconductor film such as ZnSe was grown on the substrate. In a conventional method for obtaining a compound semiconductor film having n-type conductivity, an organometallic compound containing a Group IIIb element such as Al or Ge is added to the source gas. However, the compound semiconductor film is likely to be deteriorated by the addition of the Group IIIb element as an impurity, and the compound semiconductor film is deteriorated to such an extent that it cannot be used as a blue light emitting material even at a carrier concentration of 10 17 pieces / cm 3 or less. there were.
一方，上記欠点を解消するために，第IIIb族元素の代り
に第VIIb族元素を添加する方法が採用され,HCl（塩化水
素），ZnCl2（塩化亜鉛），I2（ヨウ素）などの化合物
を原料ガス中に添加して，化合物半導体膜の成長が試み
られているが，上記のHClガスなどの水素化物を用いた
場合には，配管の機器ならびに反応容器などに対する腐
食性，および配管の内面，反応容器の内面などに対する
吸着性が強いという問題があり，また上記のZnCl,I2な
どの固体を加熱して原料ガス中に混合させる方法は，不
純物添加量の制御が極めて難しいという問題があった。On the other hand, in order to eliminate the above drawbacks, a method of adding a Group VIIb element instead of a Group IIIb element has been adopted, and compounds such as HCl (hydrogen chloride), ZnCl 2 (zinc chloride), I 2 (iodine), etc. Attempts have been made to add compound to the source gas to grow a compound semiconductor film. However, when a hydride such as HCl gas is used, the corrosiveness of piping equipment and reaction vessels and There is a problem that the adsorbability to the inner surface and the inner surface of the reaction vessel is strong, and it is extremely difficult to control the amount of impurities added in the method of heating solids such as ZnCl, I 2 and mixing them in the source gas. was there.
上述したごとく，従来技術において，第IIb族元素およ
び第VIb族元素よりなる化合物半導体膜に，不純物とし
て第IIIb族元素を添加する方法は，化合物半導体膜の劣
化が起り易く，高品質の半導体膜が得られないという欠
点があり，また不純物として第VIIb族元素の添加は,HC
l,ZnCl2，I2などの化合物を使用する関係上，腐食の問
題ならびに不純物添加量の制御が極めて難しいという問
題があった。As described above, in the prior art, a method of adding a Group IIIb element as an impurity to a compound semiconductor film composed of a Group IIb element and a Group VIb element is a method in which deterioration of the compound semiconductor film easily occurs and a high-quality semiconductor film is obtained. However, the addition of the Group VIIb element as an impurity is
Due to the use of compounds such as l, ZnCl 2 and I 2 , there were problems of corrosion and control of the amount of impurities added was extremely difficult.
本発明の目的は，上記の従来技術の欠点ならびに問題点
を解消し，不純物として添加する第VIIb族元素の添加量
の制御が極めて容易で，しかも高品質のｎ型電導性の第
IIb族元素および第VIb族元素よりなる化合物半導体膜を
成長させることのできる化合物半導体膜の製造方法を提
供することにある。The object of the present invention is to solve the above-mentioned drawbacks and problems of the prior art, to make it extremely easy to control the addition amount of the Group VIIb element added as an impurity, and to provide a high-quality n-type conductivity type element.
It is an object of the present invention to provide a method for producing a compound semiconductor film capable of growing a compound semiconductor film made of a Group IIb element and a Group VIb element.
上記目的は，化合物半導体膜の原料ガスである元素の周
期表第IIb族元素を含む化合物と第VIb族元素を含む化合
物，および化合物半導体膜に導入する不純物である第VI
Ib族元素を含む炭化水素系の化合物，例えばハロゲン化
アルキルを，キャリヤーガス（水素，アルゴンなどの不
活性ガス）によって気相で反応容器内に導入し，化学気
相反応によって第IIb族元素および第VIb族元素よりなる
化合物半導体膜を成長させることにより，達成される。The above-mentioned objects are a compound containing a Group IIb element and a compound containing a Group VIb element of the element that is the source gas of the compound semiconductor film, and an impurity that is an impurity introduced into the compound semiconductor film.
A hydrocarbon-based compound containing a Group Ib element, such as an alkyl halide, is introduced into the reaction vessel in a gas phase by a carrier gas (hydrogen, inert gas such as argon), and a Group IIb element and This is achieved by growing a compound semiconductor film made of a Group VIb element.
本発明の化合物半導体膜の製造方法は，元素の周期表第
IIb族元素および第VIb族元素からなる化合物半導体膜を
対象とするものであって，その種類として具体的にZnS,
ZnSe,ZnTe,CdS,CdSe,CdTe,HgS,HgSe,HgTeなどを挙げる
ことができる。The method of manufacturing a compound semiconductor film according to the present invention is
The object is a compound semiconductor film made of a IIb group element and a VIb group element.
Examples thereof include ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, and HgTe.
本発明の化合物半導体膜の製造方法において，導入する
不純物である第VIIb族元素を含む炭化水素系の化合物
は，ハロゲン化アルキル化合物が好ましく，ハロゲン化
アルキルを構成するハロゲン元素は，塩素，臭素，ヨウ
素のいずれかであり，上記ハロゲン化アルキルを構成す
るアルキル基は，メチル，エチル，プロピル，ブチル基
のいずれかであるハロゲン化アルキルを用いることが好
ましい。そして，ハロゲン化アルキルの他に，例えばハ
ロゲン化アリルなどの炭化水素系の化合物を用いること
もできる。In the method for producing a compound semiconductor film of the present invention, the hydrocarbon compound containing a Group VIIb element that is an impurity to be introduced is preferably an alkyl halide compound, and the halogen element constituting the alkyl halide is chlorine, bromine, It is preferable to use an alkyl halide which is any of iodine and which is one of a methyl, ethyl, propyl and butyl group as an alkyl group constituting the above alkyl halide. In addition to alkyl halides, hydrocarbon compounds such as allyl halides may be used.
以下に本発明の一実施例を挙げ，図面を参照しながらさ
らに詳細に説明する。Hereinafter, one embodiment of the present invention will be described in more detail with reference to the drawings.
第１図は本実施例において使用したZnSe化合物半導体の
単結晶膜の製造装置の構成を示す系統図である。図にお
いて,ZnSe化合物半導体の単結晶膜を構成するZn元素を
含む原料化合物である液体のジエチル亜鉛〔(C2H5)2Z
n〕が封入されているジエチル亜鉛のバブラー容器５内
に，ガス流量コントローラ９により流量調節された水素
ガス14をバブリングさせることによって，ジエチル亜鉛
を所要量含む水素ガスを形成し，これに不純物添加用の
ドーピング化合物として，ハロゲン化アルキルの１種で
あるヨウ化エチル（C2H5I）のバブラー容器７内を通過
させた所定流量の水素ガスを加えて原料ガスとなし，他
方,ZnSe化合物半導体の単結晶膜を構成すSe元素を含む
原料化合物であるセレン化水素（H2Se）が充填されてい
るセレン化水素ガスボンベ６より，流量コントローラ12
を介して所要量供給し，これにガス流量コントローラ11
から所定流量の水素ガスを加えて原料ガスとして，上記
のジエチル亜鉛およびヨウ化エチルを含む原料ガスと共
に，気相で反応容器１内に導入する。反応容器１内に
は,ZnSe化合物半導体の単結晶膜を形成させるGaAs基板
３が基板ホルダ２の上に配置されていて，高周波加熱コ
イル４により所定の温度に加熱され，化学気相反応によ
りヨウ素を含むｎ型電導性のZnSe化合物半導体の単結晶
膜がGaAs基板３上に形成される。このZnSe化合物半導体
の単結晶膜の形成において，ドーピング化合物であるヨ
ウ化エチルは常温，常圧で蒸気圧の高い液体であり，流
量コントロール10を通った水素ガスをヨウ化エチル液中
にバブリングさせるだけで，ヨウ化エチルの飽和蒸気を
含んだガスが容易に得られるので，ヨウ化エチルのバブ
ラー容器７の温度を一定に保ち，かつ流量コントロール
10でガス流量を調節することにより，ヨウ化エチルの添
加量を精密に，しかも容易に制御することが可能であ
る。FIG. 1 is a system diagram showing the configuration of a manufacturing apparatus for a ZnSe compound semiconductor single crystal film used in this example. In the figure, liquid diethylzinc [(C 2 H 5 ) 2 Z, which is a raw material compound containing the Zn element that constitutes the ZnSe compound semiconductor single crystal film, is shown.
The hydrogen gas 14 whose flow rate is adjusted by the gas flow rate controller 9 is bubbled in the diethyl zinc bubbler container 5 in which [n] is enclosed to form hydrogen gas containing a required amount of diethyl zinc, and impurities are added thereto. As a doping compound for use as a raw material gas, a predetermined flow rate of hydrogen gas passed through the bubbler container 7 of ethyl iodide (C 2 H 5 I), which is one kind of alkyl halide, was used as a source gas, while the ZnSe compound was used. From the hydrogen selenide gas cylinder 6 filled with hydrogen selenide (H 2 Se), which is a raw material compound containing Se element that constitutes a semiconductor single crystal film, to a flow rate controller 12
The required amount is supplied via the gas flow controller 11
At a predetermined flow rate, hydrogen gas is added as a raw material gas, and the raw material gas is introduced into the reaction vessel 1 in a gas phase together with the raw material gas containing diethylzinc and ethyl iodide. In the reaction vessel 1, a GaAs substrate 3 for forming a single crystal film of ZnSe compound semiconductor is placed on a substrate holder 2 and heated to a predetermined temperature by a high frequency heating coil 4, and iodine is caused by a chemical vapor reaction. A single crystal film of an n-type conductive ZnSe compound semiconductor containing is formed on the GaAs substrate 3. In the formation of this ZnSe compound semiconductor single crystal film, the doping compound ethyl iodide is a liquid with a high vapor pressure at room temperature and atmospheric pressure, and hydrogen gas that has passed through the flow rate control 10 is bubbled into the ethyl iodide liquid. A gas containing a saturated vapor of ethyl iodide can be easily obtained by using only this, so the temperature of the bubbler container 7 of ethyl iodide can be kept constant and the flow rate can be controlled.
By adjusting the gas flow rate at 10, it is possible to precisely and easily control the amount of ethyl iodide added.
以上説明した化合物半導体の単結晶膜形成装置を用い,5
℃の温度のジエチル亜鉛のバブラー容器５を通過した25
cc/分の水素ガスと,3℃の温度のヨウ化エチルのバブラ
ー容器７を通過した2cc/分の水素ガスとを,1／分の水
素ガスに混合希釈した後の原料ガスと，水素ガスで希釈
した５容積％セレン化水素ガス100cc/分の原料ガスとを
反応容器１内に導き,400℃の温度に加熱されたGaAs基板
３上に吹き付けることによりヨウ素を含むZnSe単結晶膜
を１時間当り２μｍの速度で成長させた。得られたZnSe
単結晶膜の表面は，良好な鏡面が形成され結晶性にも問
題は生じなかった。また,ZnSe単結晶膜の抵抗は，ヨウ
化エチルを添加しない場合には106Ω・cm以上の高抵抗
値であったのに対し，ヨウ化エチルを添加した場合は10
Ω・cm以下の低い抵抗値を示し,n型キャリア濃度は1018
個／cm3であった。さらに，フォトルミネッセンス特性
は,AlやGaのような従来の第IIIb族元素を添加した場合
には，キャリア濃度は1017個／cm3以上になると，結晶
欠陥が増加してその発光スペクトルは第２図の曲線15に
示すごとく，青色以外の発光が支配的になるのに対し，
本実施例の場合であるＩ濃度1018個／cm3の試料の発光
スペクトルは第２図の曲線16に示すごとく，青色発光
（約455nm付近）のみが強い極めて良好な結果が得られ
た。なお，不純物を添加する際に，不純物添加用化合物
の熱分解の容易度および不純物メモリー効果（次回の半
導体膜成長へ及ぼす影響）が重要なファクターとなる
が，本実施例においては，これらの点について何ら問題
が生じなかった。Using the compound semiconductor single crystal film forming apparatus described above,
Passed through a diethyl zinc bubbler container 5 at a temperature of 25 ° C. 25
cc / min of hydrogen gas and 2 cc / min of hydrogen gas passed through the bubbler container 7 of ethyl iodide at a temperature of 3 ° C. were mixed and diluted with 1 / min of hydrogen gas, and a raw gas and hydrogen gas 5 volume% hydrogen selenide gas diluted with 100 cc / min of raw material gas is introduced into the reaction vessel 1 and sprayed onto the GaAs substrate 3 heated to a temperature of 400 ° C. to form a ZnSe single crystal film containing iodine. It was grown at a rate of 2 μm per hour. Obtained ZnSe
A good mirror surface was formed on the surface of the single crystal film, and there was no problem in crystallinity. The resistance of the ZnSe single crystal film was as high as 10 6 Ω · cm or more when ethyl iodide was not added.
It exhibits a low resistance value of Ωcm or less, and the n-type carrier concentration is 10 18
The number was pieces / cm 3 . In addition, the photoluminescence characteristics of the conventional Group IIIb elements such as Al and Ga are such that when the carrier concentration becomes 10 17 / cm 3 or more, crystal defects increase and the emission spectrum of the element becomes As shown by the curve 15 in Fig. 2, while the light emission other than blue becomes dominant,
The emission spectrum of the sample having an I concentration of 10 18 pieces / cm 3 in the case of the present example, as shown by the curve 16 in FIG. 2, showed very good results in which only blue light emission (around 455 nm) was strong. It should be noted that, when impurities are added, the ease of thermal decomposition of the compound for impurity addition and the impurity memory effect (influence on the next semiconductor film growth) are important factors. No problems occurred about.
以上の本発明の実施例において，不純物添加用のハロゲ
ン化アルキルとしてヨウ化エチルを用いた場合の例を挙
げたが，この他に，ハロゲン元素をして塩素，臭素また
はヨウ素を有し，アルキル基として，メチル，エチル，
プロピル，ブチル基を有するハロゲン化アルキル，例え
ば塩化メチル，臭化メチル，ヨウ化メチル，塩化エチ
ル，臭化エチル，ヨウ化プロピル，ヨウ化イソプロピル
などにおいても，本実施例と同様の効果のあることを確
認している。In the above embodiments of the present invention, an example in which ethyl iodide is used as an alkyl halide for adding impurities has been described. In addition to this, an alkyl element having chlorine, bromine or iodine as a halogen element is used. As a group, methyl, ethyl,
Alkyl halides having a propyl or butyl group, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl iodide, isopropyl iodide, etc., also have the same effect as this example. Have confirmed.
また，第IIb族−第VIb族化合物半導体膜としてZnSeの場
合を例に挙げたが，これ以外の第IIb族元素と第VIb族元
素からなる化合物半導体として,ZnS,ZnTe,CdS,CdSe,CdT
e,HgS,HgSe,HgTeなどの２元系以上の化合物半導体膜の
製造においても本発明の方法が適用できることは言うま
でもない。Although ZnSe was used as an example of the Group IIb-Group VIb compound semiconductor film, ZnS, ZnTe, CdS, CdSe, CdT, and CdSe were used as compound semiconductors composed of other Group IIb elements and Group VIb elements.
It goes without saying that the method of the present invention can also be applied to the production of binary or higher compound semiconductor films such as e, HgS, HgSe, and HgTe.
以上詳細に説明したごとく，本発明の第IIb族−第VIb族
化合物半導体膜の製造方法によれば，第VIIb族元素を含
むハロゲン化アルキルなどを不純物添加用化合物として
用いるため，従来の第IIIb族元素を不純物として添加し
た場合に問題となる化合物半導体膜の劣化を抑制するこ
とができ，その結果，不純物添加濃度の高い化合物半導
体膜の結晶性を著しく向上させることができ，高品質の
ｎ型電導性の化合物半導体膜が得られる。さらに，不純
物添加用の原料ガスとして用いるハロゲン化アルキルな
どは，従来用いられていた固相の第VIIb族元素を含む原
料に比べて，不純物の添加量の制御が格段に容易とな
り，またハロゲンの水素化物を用いる場合と比較して腐
食性ならびに吸着性の問題が全く生じないという利点が
ある。As described in detail above, according to the method for manufacturing a Group IIb-Group VIb compound semiconductor film of the present invention, an alkyl halide containing a Group VIIb element or the like is used as a compound for impurity addition, and thus the conventional Group IIIb compound is used. The deterioration of the compound semiconductor film, which is a problem when the group element is added as an impurity, can be suppressed, and as a result, the crystallinity of the compound semiconductor film having a high impurity concentration can be remarkably improved and a high quality n A compound semiconductor film having type conductivity is obtained. Furthermore, in the case of alkyl halides used as source gas for impurity addition, it is much easier to control the amount of impurities added, compared to the conventionally used solid-state group VIIb element-containing materials, and the halogen Compared with the case of using a hydride, there is an advantage that there are no problems of corrosivity and adsorptivity.
第１図は本発明の実施例において用いたZnSe化合物半導
体の単結晶膜の製造装置の構成を示す系統図，第２図は
本発明の実施例において成膜したZnSe化合物半導体の単
結晶膜の室温におけるフォトルミネッセンス特性を示す
グラフである。 １…反応容器、２…基板ホルダ ３…GaAs基板、４…高周波加熱コイル ５…ジエチル亜鉛のバブラー容器 ６…セレン化水素ガスボンベ ７…ヨウ化エチルのバブラー容器 8,9,10,11,12…ガス流量コントローラ 13…排気口、14…水素ガス 15…Ga濃度1017個／cm3の試料の発光スペクトル 16…Ｉ濃度1018個／cm3の試料の発光スペクトルFIG. 1 is a systematic diagram showing the configuration of an apparatus for producing a ZnSe compound semiconductor single crystal film used in an embodiment of the present invention, and FIG. 2 is a diagram of a ZnSe compound semiconductor single crystal film formed in an embodiment of the present invention. It is a graph which shows the photoluminescence characteristic in room temperature. DESCRIPTION OF SYMBOLS 1 ... Reaction container, 2 ... Substrate holder 3 ... GaAs substrate, 4 ... High frequency heating coil 5 ... Diethyl zinc bubbler container 6 ... Hydrogen selenide gas cylinder 7 ... Ethyl iodide bubbler container 8, 9, 10, 11, 12 ... Gas flow controller 13 ... Exhaust port, 14 ... Hydrogen gas 15 ... Emission spectrum of sample with Ga concentration 10 17 pieces / cm 3 16 ... Emission spectrum of sample with I concentration 10 18 pieces / cm 3
Claims (3)
化学気相成長法によって，元素の周期表第IIb族元素お
よび第VIb族元素のうちより選ばれる少なくとも２種の
元素からなる化合物半導体膜を製造する方法において，
上記化合物半導体膜の原料ガスである第IIb族元素を含
む化合物と，第VIb族元素を含む化合物と，上記化合物
半導体膜に導入する不純物である第VIIb族元素を含む炭
化水素系の化合物を，気相で上記反応容器内に供給し
て，化学気相成長法により上記化合物半導体膜を形成さ
せることを特徴とする化合物半導体膜の製造方法。1. A compound comprising at least two elements selected from the group IIb group elements and the group VIb group elements of the periodic table by metalorganic chemical vapor deposition on a substrate placed in a reaction vessel. In a method of manufacturing a semiconductor film,
A compound containing a Group IIb element, which is a source gas of the compound semiconductor film, a compound containing a Group VIb element, and a hydrocarbon compound containing a Group VIIb element, which is an impurity introduced into the compound semiconductor film, A method for producing a compound semiconductor film, which comprises supplying the compound semiconductor film in a vapor phase to form the compound semiconductor film by a chemical vapor deposition method.
が，ハロゲン化アルキルであり，該ハロゲン化アルキル
を構成するハロゲン元素は，塩素，臭素，ヨウ素のうち
のいずれかであり，かつ上記ハロゲン化アルキルを構成
するアルキル基は，メチル基，エチル基，プロピル基，
ブチル基のうちのいずれかであるハロゲン化アルキルを
用いることを特徴とする特許請求の範囲第１項に記載の
化合物半導体膜の製造方法。2. The hydrocarbon compound containing a Group IIb element is an alkyl halide, and the halogen element constituting the alkyl halide is any one of chlorine, bromine and iodine, and The alkyl group constituting the halogenated alkyl includes a methyl group, an ethyl group, a propyl group,
The method for producing a compound semiconductor film according to claim 1, wherein an alkyl halide which is one of butyl groups is used.
元素を含む化合物，もしくは第VIIb族元素を含む炭化水
素系の化合物を，気相で反応容器内へ供給する方法が，
上記化合物を液相で容器内に充填し，該液相の化合物中
に輸送用のガスであるキャリヤーガスを通過させて，上
記液相の化合物をガス状で含むキャリヤーガスを形成
し，該液相の化合物をガス状で含むキャリヤーガスを上
記反応容器内に供給する手段によることを特徴とする特
許請求の範囲第１項または第２項に記載の化合物半導体
膜の製造方法。3. A method of supplying a compound containing a Group IIb element, a compound containing a Group VIb element, or a hydrocarbon-based compound containing a Group VIIb element into a reaction vessel in a gas phase,
The above compound is filled in a liquid phase in a container, and a carrier gas that is a gas for transportation is passed through the liquid phase compound to form a carrier gas containing the above liquid phase compound in a gaseous state. The method for producing a compound semiconductor film according to claim 1 or 2, wherein a carrier gas containing a gaseous phase compound in a gaseous state is supplied into the reaction vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27169686A JPH0740560B2 (en) | 1986-11-17 | 1986-11-17 | Method for manufacturing compound semiconductor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27169686A JPH0740560B2 (en) | 1986-11-17 | 1986-11-17 | Method for manufacturing compound semiconductor film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126235A JPS63126235A (en) | 1988-05-30 |
| JPH0740560B2 true JPH0740560B2 (en) | 1995-05-01 |
Family
ID=17503567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27169686A Expired - Lifetime JPH0740560B2 (en) | 1986-11-17 | 1986-11-17 | Method for manufacturing compound semiconductor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0740560B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61164228A (en) * | 1985-01-16 | 1986-07-24 | Seiko Epson Corp | Method for producing Group 2-6 compound semiconductor thin film |
-
1986
- 1986-11-17 JP JP27169686A patent/JPH0740560B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61164228A (en) * | 1985-01-16 | 1986-07-24 | Seiko Epson Corp | Method for producing Group 2-6 compound semiconductor thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63126235A (en) | 1988-05-30 |
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