JPS5863128A - Manufacture of thin film semiconductor - Google Patents

Manufacture of thin film semiconductor

Info

Publication number
JPS5863128A
JPS5863128A JP56161428A JP16142881A JPS5863128A JP S5863128 A JPS5863128 A JP S5863128A JP 56161428 A JP56161428 A JP 56161428A JP 16142881 A JP16142881 A JP 16142881A JP S5863128 A JPS5863128 A JP S5863128A
Authority
JP
Japan
Prior art keywords
thin film
gas
germanium
hydrogen
film semiconductor
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.)
Granted
Application number
JP56161428A
Other languages
Japanese (ja)
Other versions
JPS6157694B2 (en
Inventor
Kazu Yamanaka
山中　計
Takeshi Aragai
新貝　健
Masahiro Hotta
堀田　正裕
Toshio Kamisaka
上坂　外志夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP56161428A priority Critical patent/JPS5863128A/en
Publication of JPS5863128A publication Critical patent/JPS5863128A/en
Publication of JPS6157694B2 publication Critical patent/JPS6157694B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
    • H10P14/2901—Materials
    • H10P14/2902—Materials being Group IVA materials
    • H10P14/2905—Silicon, silicon germanium or germanium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/22—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using physical deposition, e.g. vacuum deposition or sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/27—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using selective deposition, e.g. simultaneous growth of monocrystalline and non-monocrystalline semiconductor materials
    • H10P14/271—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using selective deposition, e.g. simultaneous growth of monocrystalline and non-monocrystalline semiconductor materials characterised by the preparation of substrate for selective deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
    • H10P14/3411—Silicon, silicon germanium or germanium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3438—Doping during depositing
    • H10P14/3441—Conductivity type
    • H10P14/3442—N-type
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3438—Doping during depositing
    • H10P14/3441—Conductivity type
    • H10P14/3444—P-type

Landscapes

  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Photovoltaic Devices (AREA)

Abstract

PURPOSE:To simply and continuously obtain the titled thin film semiconductor of high quality as well as to enable to easily form them into a large area by a method wherein, in the case of the thin film semiconductors to be used for photoelectromotive elements, a germanium ion and a specific gas ion are collided with an electrode substrate under the condition of high vacuum by applying high emergy. CONSTITUTION:Polycrystalline germanium is fed to the crucible 141 of an electron beam evaporating source 14, and then air is exhausted from an air exhaust port 13 by a device on the exhaust system. When the degree of vacuum has been stabilized, one of hydrogen gas, the mixed gas of hydrogen and diborane and the mixed gas of hydrogen and phosphine is introduced from a gas introducing pipe 16 by adjusting valves 26-29 in such a manner that the partial pressure thereof will become in the range of 8X10<-4>Torr. to 1X10<-5>Torr. High energy is given to an ion by applying negative DC high voltage to a substrate holder 18 from a power source 22, the ion is incidented on the surface of an electrode substrate 19, and through these procedures the amorphous germanium thin film, which is a thin film semiconductor, can be formed.

Description

【発明の詳細な説明】 本発明はゲルマニウム薄膜半導体とくに光起電力素子用
の薄膜半導体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing germanium thin film semiconductors, particularly thin film semiconductors for photovoltaic devices.

従来、光起電力素子用のゲルマニウム半導体の製造方法
としては、ゲルマニウム溶融体がら結晶成長させた単結
晶等を基板としてこの基板に不純物の拡散等を施こす方
法やＧｅＨ４に不純物を添加したガス中のグロー放電に
より不純物制御された非晶質ゲルマニウム半導体Ｍｔ膜
を形成させる方法等が知られている。しがしながら、単
結晶を基板とする前者の場合は、単結晶を形成させる段
階および光起電力素子を形成する段階において複雑な工
程を必要とするため、得られる光電素子は非常に高価な
ものになるという問題点があった。Conventionally, methods for manufacturing germanium semiconductors for photovoltaic devices include methods such as using a single crystal grown from a germanium melt as a substrate and diffusing impurities onto this substrate, or using GeH4 in a gas doped with impurities. A method of forming an amorphous germanium semiconductor Mt film with controlled impurities using glow discharge is known. However, in the former case where a single crystal is used as a substrate, complicated steps are required in the steps of forming the single crystal and forming the photovoltaic device, so the resulting photovoltaic device is very expensive. There was a problem with it becoming a thing.

一方、ＧｅＨ４のグロー放電分解法で作成される非晶質
ゲルマニウムを用いる後者の方法は薄膜化が容易なため
、数ミクロンのものの作成が可能であり、原材料や電力
エネルギーが少なくて済み、且つ結晶質半導体では困難
であった連続生産や大面積化も可能である。そして該非
晶質半導体の形成方法としてはグロー放電分解法が広く
採用されているが、そのほかにスパッタリング法が提案
されている。しかしながら、グロー放電分解法及びスパ
ッタリング法はともに数トールから１０”トール程度の
比較的真空度の低い低圧雰囲気中に於るプラズマを利用
しているため、形成されるゲルマニウム膜の膜質が悪く
なったり、又、プラズマ制御の困難性から生ずる物性上
のバラツキや不均一性が生じる等の難点を有し、廉価な
光起電力素子を大面積で連続生産するには、未だ解決し
なければならない問題点を多く残していた。On the other hand, the latter method, which uses amorphous germanium produced by the glow discharge decomposition method of GeH4, is easy to make into thin films, so it is possible to create a film with a thickness of several microns, requiring less raw materials and electrical energy, and is crystalline. Continuous production and large-area production, which is difficult with high-quality semiconductors, are also possible. The glow discharge decomposition method is widely used as a method for forming the amorphous semiconductor, but a sputtering method has also been proposed. However, since both the glow discharge decomposition method and the sputtering method utilize plasma in a relatively low vacuum atmosphere of several torr to 10" torr, the quality of the germanium film formed may be poor. In addition, it has drawbacks such as variations in physical properties and non-uniformity due to the difficulty of plasma control, and this problem still needs to be solved in order to continuously produce inexpensive photovoltaic devices over a large area. He left a lot of points.

本発明は上記グロー放電法及びスパッタリング法による
非晶質ゲルマニウム薄膜半導体の製造方法に於る問題点
を解消して、とくに光起電力素子として品質のすぐれた
非晶質ゲルマニウム薄膜半導体を連続的に生産出来、し
かも大面積化が可能な薄膜半導体の製造方法を提供する
３− ことを目的としてなされたものである。The present invention solves the problems in the method for manufacturing amorphous germanium thin film semiconductors using the glow discharge method and sputtering method, and enables continuous production of amorphous germanium thin film semiconductors of excellent quality, especially as photovoltaic devices. The purpose of this invention is to provide a method for manufacturing thin film semiconductors that can be produced and made larger in area.

すなわち本発明の要旨は、１０−”　トール以Ｔの高真
空に排気された真空容器内に、８　Ｘ　１０−’トール
からｌＸｌ０−５）−ルの範囲の分圧を有する様に、水
素ガス、水素とジボランとの混合ガス、及び水素とホス
フィンとの混合ガスからなる群から選ばれたガスを導入
し、該導入されたガスと、ゲルマニウムを加熱蒸発する
ことにより得られるゲルマニウム単原子とに加速電子を
衝突させて電離若しくは解離させ、かくして生成したガ
スイオン及びゲルマニウムイオンに電界効果により高エ
ネルギーを付与させて゛磁極基板上に射突させ、薄膜ゲ
ルマニウムを形成することを特徴とする薄膜半導体の製
造方法に存する。That is, the gist of the present invention is to introduce hydrogen gas into a vacuum container evacuated to a high vacuum of less than 10 torr so as to have a partial pressure in the range of 8 , a gas selected from the group consisting of a mixed gas of hydrogen and diborane, and a mixed gas of hydrogen and phosphine is introduced, and the introduced gas is combined with germanium monoatoms obtained by heating and evaporating germanium. A thin film semiconductor characterized by colliding accelerated electrons to cause ionization or dissociation, imparting high energy to the gas ions and germanium ions thus generated by an electric field effect, and making them impinge on a magnetic pole substrate to form a thin film of germanium. It depends on the manufacturing method.

以下図面を参照しながら本発明の薄膜半導体の製造方法
番こついて説′：１１明する。The method for manufacturing a thin film semiconductor according to the present invention will be explained below with reference to the drawings.

第１図は本発明方法で製造された薄膜半導体が用いられ
た光起電力素子の一例を示す断面図で該素子はショット
キーバリア型のものであり、４− 図中１？ｉ基材であり、該基材としては例えば、ポリ塩
化ビニル、ポリフッ化ビニル、酢酸セルロース、ポリエ
チレンテレフタレート、ポリブチレンテレフタレート、
ポリエチレン、ポリプロピレン、ポリカーボネート、ポ
リイミド、ポリエーテルサルフオン、ポリパラバン酸等
の高分子材料、ガラス、磁器、陶器等のセラミック材料
或いはアルミニウム、ステンレススチール等の金属材料
などのフィルム状物又は薄板状物から構成される。２は
基材端子電極であり、該基板端子電極２Ｆｉその上に形
成される薄膜半導体層３に対してオルミックコンタクト
が得られるような金属材料で形成されており、該形成は
通常金属蒸着の手法によって行われる。FIG. 1 is a cross-sectional view showing an example of a photovoltaic device using a thin film semiconductor manufactured by the method of the present invention, and the device is of a Schottky barrier type. i base material, such as polyvinyl chloride, polyvinyl fluoride, cellulose acetate, polyethylene terephthalate, polybutylene terephthalate,
Consists of film-like or thin plate-like materials such as polymer materials such as polyethylene, polypropylene, polycarbonate, polyimide, polyether sulfone, and polyparabanic acid, ceramic materials such as glass, porcelain, and ceramics, or metal materials such as aluminum and stainless steel. be done. Reference numeral 2 denotes a base terminal electrode, which is made of a metal material that can provide ohmic contact with the thin film semiconductor layer 3 formed on the base terminal electrode 2Fi, and is usually formed by metal vapor deposition. It is done by method.

そして上記金属材料としては、その上に形成される薄膜
半導体層３がｎ型非晶質ゲルマニウムである場合はステ
ンレス等を含む金属材料が好ましい。上記基材１と基板
端子電極２とにより電極基板が形成される。薄膜半導体
層３＃−ｉ本発明方法により形成される非晶質ゲルマニ
ウム５− よりなる層であり、該層はｎ型若しくけＰ型半導体とな
されるか若しくけ、真性半導体、ｎ型半導体及びＰ型半
導体の三者の中の三者以上が適宜組合わされて積層され
たものである。When the thin film semiconductor layer 3 formed thereon is n-type amorphous germanium, the metal material is preferably a metal material including stainless steel or the like. An electrode substrate is formed by the base material 1 and the substrate terminal electrode 2. Thin film semiconductor layer 3#-i A layer made of amorphous germanium 5- formed by the method of the present invention, and the layer may be an n-type or p-type semiconductor, or may be an intrinsic semiconductor, an n-type Three or more of the three semiconductors and P-type semiconductors are laminated in appropriate combinations.

薄膜半導体層３をｎ型のものとするには本発明方法にお
いて導入するガスとして水素とホスフィンからなる混合
ガスを用いればよく、Ｐ型のものとするには水素とジボ
ランとの混合ガスを用いればよく、又真性半導体とする
には導入ガスとして水素のみを用いればよい。又、本発
明において導入ガスを逐次切換えることにより、使用し
た導入ガスの種類に対応した２種以上の型の半導体層が
積層された積層半導体層を得ることが出来る。To make the thin film semiconductor layer 3 n-type, a mixed gas of hydrogen and phosphine may be used as the gas introduced in the method of the present invention, and to make it p-type, a mixed gas of hydrogen and diborane may be used. In addition, only hydrogen may be used as the introduced gas to form an intrinsic semiconductor. Further, in the present invention, by sequentially switching the introduced gas, it is possible to obtain a laminated semiconductor layer in which two or more types of semiconductor layers corresponding to the type of introduced gas used are laminated.

又、＃膜半導体層３の厚さは数千オングストロームから
数ミクロンのオーダーの範囲とするのが好ましい。Further, the thickness of the # film semiconductor layer 3 is preferably in the range of the order of several thousand angstroms to several microns.

次に第１図において４は薄膜半導体／ｉ＠３との間でシ
ョットキーバリアを形成する金属薄膜であり、該薄膜４
ｔｆ１００オングストロームから６− 数ミクロンの範囲の厚さに蒸着されて形成されるのがよ
い。そして該薄膜４を構成する金属材料としてはプラチ
ナや金等が好適である。金属薄膜４上にはクシ形又は線
状等の構造の電流収集用の対向端子電極５が配置されて
おり、又、６は必要に応じて最上層に蒸着形成などによ
って設けられてもよい反射防止膜である。Next, in FIG. 1, 4 is a metal thin film that forms a Schottky barrier between the thin film semiconductor/i@3;
tf is preferably deposited to a thickness ranging from 100 angstroms to 6 to several microns. The metal material constituting the thin film 4 is preferably platinum, gold, or the like. On the metal thin film 4, a counter terminal electrode 5 having a comb-shaped or linear structure for collecting current is arranged, and if necessary, a reflective electrode 6 may be provided on the top layer by vapor deposition or the like. It is a preventive film.

本発明で製造された薄膜半導体の光起電力素子への適用
例として第１図を示したが、これに限定されることはな
く他の形式の光起電力素子に適用することも可能である
。Although FIG. 1 is shown as an example of application of the thin film semiconductor manufactured by the present invention to a photovoltaic device, the present invention is not limited thereto and can be applied to other types of photovoltaic devices. .

次に、本発明方法を実施するための装置の一例を示す第
２図にもとずいて説明するに、第２図に示される装置に
おいては、 真空槽ｌｌ内の真空室１２Ｆｉ排気口１３に連結される
排気系装置（油回転ポンプ、油拡散ポンプ等で構成され
ているが、図示されていない）によってｌＸ１０’トー
ルまでの高真空に排気されることが可能になされており
、そして真空室１２には電子ビーム蒸発源１４（電源回
路等は図示されていない）邪魔板１５、ループ状のガス
導入管１６、電子発生装置１１７．基板ホルダー１８、
及びそれに取り付けられた電極基板１９が設置されてお
り、更に真空槽１１の外方には、装置を動作させるため
の電源２０〜２２とその回路、ループ状ガス導入管１６
にバルブ２６〜２９１こよって切換及び流量調節可能に
接続された水素、ジボラン、ホスフィンがそれぞれ充填
されたボンベ２３，２４．２５が設置されている。Next, an explanation will be given based on FIG. 2 showing an example of an apparatus for carrying out the method of the present invention. In the apparatus shown in FIG. A connected exhaust system device (composed of an oil rotary pump, an oil diffusion pump, etc., not shown) makes it possible to exhaust to a high vacuum of up to 10' Torr, and the vacuum chamber 12 includes an electron beam evaporation source 14 (power supply circuit etc. not shown) baffle plate 15, loop-shaped gas introduction pipe 16, electron generator 117. board holder 18,
and an electrode substrate 19 attached thereto, and further outside the vacuum chamber 11 are power supplies 20 to 22 and their circuits for operating the device, and a loop-shaped gas introduction pipe 16.
There are installed cylinders 23, 24, and 25 filled with hydrogen, diborane, and phosphine, respectively, which are connected to the cylinders 26 to 291 so that they can be switched and whose flow rates can be adjusted.

本発明にもとすいて薄膜半導体を製造するには、第２図
に示す様に電極基板１９を基板ホルダー１８に配置し、
電子ビーム蒸発源１４のルツボ１４１１こ多結晶ゲルマ
ニウムを供給し、次いで排気口１３から排気系装置−ζ
よって排気を行なって真空窒化よって排気を行なって真
空室１２をｌＸｌ０’）−ル好ましくＨＩＸＩ□−７ト
ールよりも高度の高真空となし、真空度が安定したとこ
ろでガス導入管１６よりバルブ２６〜２９を調節しなが
ら、水素、水素とジボランとの混合ガス、又は水素とホ
スフィンとの混合ガスの３者のうちのいずれかを分圧が
８Ｘ１０−４トールから１×１０″−１１トールの範囲
になる様に導入する。In order to manufacture a thin film semiconductor according to the present invention, an electrode substrate 19 is placed on a substrate holder 18 as shown in FIG.
Polycrystalline germanium is supplied to the crucible 1411 of the electron beam evaporation source 14, and then the exhaust system device -ζ is supplied from the exhaust port 13.
Therefore, the vacuum chamber 12 is evacuated by vacuum nitriding to create a high vacuum, preferably higher than HIXI□-7 Torr, and when the degree of vacuum is stabilized, the gas inlet pipe 16 is opened to the valve 26 to While adjusting Introduce it so that it becomes.

上記導入されるガスの種類については、目的とする半導
体の種類によって選択される。The type of gas introduced above is selected depending on the type of target semiconductor.

なお、混合ガスの場合は水素分圧対ジボラン又はホスフ
ィン分圧の割合が１：（１０５〜３となる様にするのが
好ましい。次いで電子ビーム蒸発源１４を動作させてル
ツボ１４１内のゲルマニウムを蒸気化させ、該ゲルマニ
ウムの原子状粒子と導入された水素又は混合ガスを電子
発生装ｖｊ１１７からの高速電子により衝突電離若しく
は解離せしめてイオン化させる。In the case of a mixed gas, it is preferable that the ratio of hydrogen partial pressure to diborane or phosphine partial pressure is 1:(105 to 3).Then, the electron beam evaporation source 14 is operated to evaporate germanium in the crucible 141. The atomic particles of germanium and the introduced hydrogen or mixed gas are ionized by impact ionization or dissociation by high-speed electrons from an electron generator vj117.

なお、電子発生装Ｗ１７Ｆｉフィラメント１７１、メツ
シュ状電極１７２及びガート電極１７３から構成されて
おり、本実施例では電源２１により一６００ｖの直流電
位を与えられたフィラメント１７１に、電源２０１コよ
りＩＯＶ、３０Ａの交流電流を通電し加熱せしめ熱電子
を発生さ９− せると共にメツシュ状電極１７２を接地することにより
上記熱電子を電界加速させて高速電子を発生するｉｌこ
なされている。The electron generator is composed of a W17Fi filament 171, a mesh electrode 172, and a guard electrode 173. In this embodiment, the filament 171 is supplied with a DC potential of -600V by the power supply 21, and the IOV, 30A is applied from the power supply 201. An alternating current is applied to generate heat to generate hot electrons, and the mesh electrode 172 is grounded to accelerate the hot electrons with an electric field to generate high-speed electrons.

前記によりイオン化されたガスイオン及びゲルマニウム
イオンに対し、基板ホルダー１８に電源２２１こより負
の直流高電圧を印加することで高エネルギーを付与し、
電極基板１９表面に入射せしめ、かくして薄膜半導体で
ある非晶質のゲルマニウム薄膜を形成させるのである。High energy is imparted to the ionized gas ions and germanium ions by applying a negative DC high voltage from the power source 221 to the substrate holder 18,
The light is made incident on the surface of the electrode substrate 19, thus forming an amorphous germanium thin film which is a thin film semiconductor.

しかして本発明における高エネルギーとしては、運動エ
ネルギーが常温に於て１０ｅＶから８ＫｅＶまでの範囲
のものが好適であり、この様な高エネルギーかイ」与さ
れたゲルマニウムイオン及びガスイオンが基板１９表面
１こ入射されることにより、半導体としての性能を有す
る非晶質のゲルマニウム薄膜が形成されるのである。又
、高エネルギーを付与するために基板ホルダー１８に印
加される負の直流電圧は次式を満足するのがよい。Therefore, as the high energy in the present invention, it is preferable that the kinetic energy is in the range of 10 eV to 8 KeV at room temperature, and the germanium ions and gas ions given with such high energy are distributed on the surface of the substrate 19. By irradiating a single beam, an amorphous germanium thin film with semiconductor performance is formed. Further, it is preferable that the negative DC voltage applied to the substrate holder 18 to impart high energy satisfies the following equation.

０．０１≦１Ｖａｌ≦ＩＱＯ−−ＴＳ ４ １０− （但し、Ｖａは印加される負の直流電圧（ＫＶ）　。0.01≦1Val≦IQO--TS 4 10- (However, Va is the applied negative DC voltage (KV).

ＴＳは基板温度（０Ｋ）である。） 本発明の薄膜半導体の製造方法は上述の通りの方法であ
り、高真空の条件下でゲルマニウムイオン及び特定のガ
スイオンに高エネルギーを付与させて電極基板上に射突
させることにより非晶質ゲルマニウムからなる薄膜を形
成させることにより、特に光起電力素子としてすぐれた
性質の半導体を高品質で簡単にしかも連続的に得ること
が出来、さらに大面積化も容易なるものである。又、導
入ガスの種類を選択することによって、ｎ型、Ｐ型等の
半導体を自在に作り分けることが出来、異なったタイプ
の半導体が積層された積層タイプの半導体を製造するこ
とも簡単に出来る。TS is the substrate temperature (0K). ) The method for manufacturing a thin film semiconductor of the present invention is as described above, and is made by imparting high energy to germanium ions and specific gas ions and making them impinge on an electrode substrate under high vacuum conditions. By forming a thin film made of germanium, it is possible to easily and continuously obtain a high-quality semiconductor with excellent properties, especially as a photovoltaic device, and it is also easy to increase the area. Furthermore, by selecting the type of introduced gas, it is possible to freely produce semiconductors such as n-type and p-type, and it is also possible to easily produce a laminated type semiconductor in which different types of semiconductors are laminated. .

【図面の簡単な説明】[Brief explanation of drawings]

第１図は、本発明方法で製侍された薄膜半導体が用いら
れた光起電力素子の一例を示す断面図、第２図は本発明
方法を実施するための装置の一例を示す説明図である。 層、４・・・金属薄膜、５・・・対向端子電極、６・・
・反射防止膜、１２・・・真空室、１４・・・電子ビー
ム蒸発源、１６・・・ループ状ガス導入管、１７・・・
電子発生装置、１８・・・基板ホルダー、１９・・・電
極基板、２０〜２２・・・電源、２３〜２５・・・ボン
ベ、２６〜２９・・・バルブ 特許出願人 積水化学工業株式会社 代表者藤沼基利 ′１FIG. 1 is a cross-sectional view showing an example of a photovoltaic device using a thin film semiconductor manufactured by the method of the present invention, and FIG. 2 is an explanatory diagram showing an example of an apparatus for carrying out the method of the present invention. be. Layer, 4... Metal thin film, 5... Opposing terminal electrode, 6...
・Anti-reflection film, 12... Vacuum chamber, 14... Electron beam evaporation source, 16... Loop-shaped gas introduction tube, 17...
Electron generator, 18... Substrate holder, 19... Electrode substrate, 20-22... Power supply, 23-25... Cylinder, 26-29... Valve Patent applicant Sekisui Chemical Co., Ltd. representative Mototoshi Fujinuma'1

Claims (1)

【特許請求の範囲】 ＬＩＯ−５トール以下の高真空に排気された真空容器内
に、８Ｘ１０−’ｌ−−ルからＩ　Ｘ　１０−５トール
の部門の分圧を有する様に、水素ガス、水素とジボラン
との混合ガス、及び水素とホスフィンとの混合ガスから
なる群から選ばれたガスを導入し、該導入されたガスと
、ゲルマニウムを加熱蒸発することにより得られるゲル
マニウム単原子とに加速電子を衝突させて電離若しくけ
解離させ、かくして生成したガスイオン及びゲルマニウ
ムイオンに電界効果により高エネルギーを付与させて電
極基板上に射突させ、薄膜ゲルマニウムを形成すること
を特徴とする薄膜半導体の製造方法。 ス　ガスイオン及びゲルマニウムイオンに付与される高
エネルギーが１０　ｅＶから８　ＫｅＶの範囲である第
１項記載の薄膜半導体の製造方法。[Claims] In a vacuum vessel evacuated to a high vacuum of less than LIO-5 torr, hydrogen gas, having a partial pressure in the division from 8 x 10-'l to I x 10-5 torr, A gas selected from the group consisting of a mixed gas of hydrogen and diborane and a mixed gas of hydrogen and phosphine is introduced, and the introduced gas is accelerated to germanium single atoms obtained by heating and evaporating germanium. A thin film semiconductor characterized by colliding electrons to cause ionization or dissociation, imparting high energy to the thus generated gas ions and germanium ions by an electric field effect, and causing them to impinge on an electrode substrate to form a thin film of germanium. manufacturing method. 2. The method for producing a thin film semiconductor according to claim 1, wherein the high energy imparted to the gas ions and germanium ions is in the range of 10 eV to 8 KeV.
JP56161428A 1981-10-09 1981-10-09 Manufacture of thin film semiconductor Granted JPS5863128A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP56161428A JPS5863128A (en) 1981-10-09 1981-10-09 Manufacture of thin film semiconductor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP56161428A JPS5863128A (en) 1981-10-09 1981-10-09 Manufacture of thin film semiconductor

Publications (2)

Publication Number Publication Date
JPS5863128A true JPS5863128A (en) 1983-04-14
JPS6157694B2 JPS6157694B2 (en) 1986-12-08

Family

ID=15734915

Family Applications (1)

Application Number Title Priority Date Filing Date
JP56161428A Granted JPS5863128A (en) 1981-10-09 1981-10-09 Manufacture of thin film semiconductor

Country Status (1)

Country Link
JP (1) JPS5863128A (en)

Also Published As

Publication number Publication date
JPS6157694B2 (en) 1986-12-08

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