JPH01307229A - Deposited film formation method - Google Patents

Abstract

PURPOSE:To prevent the attaching of a coating film or powder to the inner wall of a discharging pipe or deposition chamber by supplying ClF3 to the discharging channel of a discharging system, at the time of forming a deposition film. CONSTITUTION:At the same time when a deposition film is started to be formed, an ON-OFF valve 132 is opened, and a specified amount of gas containing at least ClF3 gas is supplied to a discharging pipe 143, from a gas cylinder in which gas containing at least ClF3 is filled, via a pressure reducing equipment 133 and a mass flow controller 134. After the deposition film is formed, the supply of film forming gas and the gas containing at least ClF3 is interrupted, and a substrate 104 is taken out by making a reaction vessel 101 leak after the inside of a system is purged. The gas containing ClF3 acts with reaction product attaching to the discharging pipe 141, returns it to vapor phase, and turns precursor, which flows from a reaction vessel 101 and turns to the origin of reaction product, into the gas of single substance silicon compound. This gas is discharged by an exhaust pump 143, thereby, preventing the attaching of the reaction product such as polysilane to the inner wall of discharging pipe.

Description

Translated fromJapanese

【発明の詳細な説明】〔産業上の利用分野〕本発明はプラズマＣｖ法や光ＣＶＤ法など気相反ろによ
シリコン系堆積膜を基板上に形成する堆積膜形成法の改
良に関し、とくに排気系のりＩＪ−ニング方法を改良し
た堆積膜形成法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improvement in a deposited film forming method for forming a silicon-based deposited film on a substrate by vapor phase filtration, such as plasma CV method or photo CVD method, and in particular, The present invention relates to a deposited film forming method that is an improved IJ-based gluing method.

〔従来の技術〕[Conventional technology]

気相法により基板上にシリコン系堆積膜等の機能性堆積
膜を形成する技術は、たとえば電子写真用像形成部材及
び太陽電池等の光導電部材やＴＰＴ等の半導体素子を製
造する場合などに既に広く採用されている。The technology of forming a functional deposited film such as a silicon-based deposited film on a substrate by a vapor phase method is used, for example, in the production of electrophotographic image forming members, photoconductive members such as solar cells, and semiconductor elements such as TPT. It has already been widely adopted.

このような気相法による堆積膜形成法によれば、反応生
成物の一部が目的とする基板以外の部分、すなわち排気
管や堆積室等の内壁に被膜又は粉末として付着すること
が避けられない・このうち特に排気管の内壁に付着した被膜や粉末は、排
気管の実質的な排気抵抗を増大させる原因となり、成膜
時の堆積室内の圧力変動を生じさせる結果、形成された
堆積膜の品質及び特性の安定性を損ねるという問題点が
あった。According to such a deposition film formation method using a vapor phase method, it is possible to avoid a part of the reaction product from adhering as a film or powder to parts other than the target substrate, that is, the inner walls of the exhaust pipe, deposition chamber, etc. - Among these, films and powders that adhere to the inner wall of the exhaust pipe cause an increase in the effective exhaust resistance of the exhaust pipe, causing pressure fluctuations in the deposition chamber during film formation, and as a result, the deposited film formed There was a problem in that the quality and stability of properties were impaired.

この問題点を解決するための手段として、排気手段にた
とえばメカニカル・ブースター・４ンプなどの排気速度
可変型真空排気ポンプを使用し、成膜時の堆積室内の圧
力をモニターしながら、それが一定となるように該−ン
プの排気速度を変化させる方法が知られている。As a means to solve this problem, a variable speed vacuum pump such as a mechanical booster 4 pump is used as the evacuation means, and the pressure inside the deposition chamber is monitored during film formation to ensure that it remains constant. A method is known in which the exhaust speed of the pump is changed so that

しかしながら、この方法では前記ポンプ及び堆積室内の
圧力をモニターし排気速度を変化させ堆積室内の圧力が
一定となるようフィードバックするシステムに多額の費
用が必要となシ、その結果、堆積膜の製品コストを上昇
させる欠点がある。However, this method requires a large amount of money for the pump and a system that monitors the pressure in the deposition chamber, changes the pumping speed, and provides feedback so that the pressure in the deposition chamber is constant, and as a result, the product cost of the deposited film increases. It has the disadvantage of increasing

また、前記問題点の別の解決手段として、排気管にクリ
ーニング用のガスの供給口、たとえばＣＦ４やＮＦ３等
のＡわゆるエツチングガスの供給口を設け、この供給口
からエツチングガスを供給するとともに、該供給口と排
気手段との間にたとえばグロー放電等のガス分解手段を
用いてこのエツチングガスを分解し、排気管の内壁に付
着していた被膜や粉末と反応せしめ、気相に戻して排気
させ一以って排気管内壁をクリーニングして排気抵抗の
一定化を図シ、内圧を一定にする方法も知られている。As another solution to the above problem, the exhaust pipe is provided with a cleaning gas supply port, for example, a so-called etching gas supply port such as CF4 or NF3, and the etching gas is supplied from this supply port. The etching gas is decomposed using a gas decomposition means such as glow discharge between the supply port and the exhaust means, reacts with the film or powder adhering to the inner wall of the exhaust pipe, and returns to the gas phase. A method is also known in which the internal pressure is kept constant by cleaning the inner wall of the exhaust pipe after exhausting the gas to make the exhaust resistance constant.

しかし、この方法では排気管に供給し九エッチングブス
の分解手段、たとえばグロー放電等のエネルギー供給手
段を必要とするため、装置を複雑化するとともＫこれも
堆積膜の製品コストを上昇させる問題点が残る・〔発明の目的〕本発明の目的は、気相法によシ基板上に堆積膜を形成す
る方法において、排気路内壁に付着する被膜又は粉末が
もたらす堆積室内の圧力変動を低コストで抑制すること
ができ、且つ堆積膜の品質及び特性を安定化させる堆積
膜形成法を提供することＫある。However, this method requires an energy supply means such as glow discharge to be supplied to the exhaust pipe and to decompose the etching bus, which makes the equipment complicated and also increases the cost of the deposited film product. [Objective of the Invention] The object of the present invention is to reduce the pressure fluctuations in the deposition chamber caused by the coating or powder adhering to the inner wall of the exhaust passage at low cost in a method of forming a deposited film on a substrate by a vapor phase method. It is an object of the present invention to provide a method for forming a deposited film that can suppress the damage caused by the oxidation and stabilize the quality and characteristics of the deposited film.

〔問題点を解決するための手段及び作用〕本発明は、気
相法によシ基体上に堆積膜を形成するための堆積室と該
室内を排気するための排気系とを備えた堆積膜形成装置
ｆ、用いる堆積膜形成法において、堆積膜形成時に、前
記排気系の排気路にＣｔＶ、を供給することを特徴とす
る。[Means and effects for solving the problems] The present invention provides a deposited film comprising a deposition chamber for forming a deposited film on a substrate by a vapor phase method and an exhaust system for exhausting the interior of the chamber. The deposited film forming method used in the forming apparatus f is characterized in that CtV is supplied to the exhaust path of the exhaust system when forming the deposited film.

すなわち、本発明はプラズマや熱などエネルギー供給手
段を用いることなく、排気路内壁のクリーニングを可能
とするものである。前記ガス供給口から供給されたＣｌ
Ｆ３ガスは反応性が高く、外部からエネルギーを供給し
なくても常温でポリシランと反応し、反応生成物を５Ｉ
Ｆ４．　ＳｉＦ、（ｔ・・・・・・などのシリコン系化
合物として気相に戻せる丸め、排気系の乾式クリーニン
グが可能となる。That is, the present invention makes it possible to clean the inner wall of the exhaust passage without using energy supply means such as plasma or heat. Cl supplied from the gas supply port
F3 gas is highly reactive and reacts with polysilane at room temperature without external energy supply, converting the reaction product into 5I
F4. It is possible to dry clean the exhaust system by rolling it back into the gas phase as a silicon-based compound such as SiF or (t...).

以下、図面を参照しながら本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to the drawings.

第１図は、気相法で堆積膜を形成するための堆積膜形成
装置の一例を示すものである。同図において、１０１は
堆積膜形成用の反応槽で、この中には成膜用ガ♂放出口
１０２、グロー放電を生起させるための電極１０３、基
板１０４が設けられている。１０５は電極１０３に連絡
されたグロー放電生起用高周波電源、１０６は真空計、
１０７は基板加熱用ヒーター、１０８はヒーター用電源
である。また、１１１及び１２１は堆積膜形成用Ｏ原料
ガス、あるいは希釈ガス、ドーピングがス、たとえば５
ＩＨ４ｐ　Ｓｉ２Ｈ６ｓ　Ｇｅｍ４．Ｈ２ｔ　Ａｒ　ｓ
　Ｂ２Ｈ６゜ＰＨ３等が充填されたボンベであり、１１
２と１２２はそれぞれがンベの開閉パルプ、１１３と１
２３はいづれもガス圧力を必要な値まで下げるための減
圧装置、１１４と１２４は各々ガス流量を制御するため
のマスフローコントローラーである。FIG. 1 shows an example of a deposited film forming apparatus for forming a deposited film by a vapor phase method. In the figure, 101 is a reaction tank for forming a deposited film, in which a gas discharge port 102 for film formation, an electrode 103 for generating glow discharge, and a substrate 104 are provided. 105 is a high frequency power source for generating glow discharge connected to the electrode 103; 106 is a vacuum gauge;
107 is a heater for heating the substrate, and 108 is a power source for the heater. Further, 111 and 121 are O source gas for forming the deposited film, dilution gas, doping gas, for example, 5
IH4p Si2H6s Gem4. H2t Ar s
It is a cylinder filled with B2H6゜PH3 etc., and 11
2 and 122 are the opening and closing pulp of Nbe, 113 and 1 respectively.
23 are pressure reducing devices for lowering the gas pressure to a required value, and 114 and 124 are mass flow controllers for controlling the gas flow rate.

１４１は反応ｌｌ１１０１を真空にする際に用いる排気
管、１４２は排気パルプ、１４３は排気ポンプである。141 is an exhaust pipe used to evacuate the reaction 1101, 142 is an exhaust pulp, and 143 is an exhaust pump.

また、１３１は少なくともＣ１Ｆ、を含むガスが充填さ
れたボンベ、１３２はボンベ（７）開閉パルプ、１３３
はガス圧力を所定の値にまで下げるための減圧器、１３
４はガス流量を制御するためのマスフローコントローラ
ーである。Further, 131 is a cylinder filled with a gas containing at least C1F, 132 is a cylinder (7) for opening/closing pulp, and 133
is a pressure reducer for lowering the gas pressure to a predetermined value, 13
4 is a mass flow controller for controlling the gas flow rate.

次に、上述した堆積膜形成装置の作用もしくは操作方法
について具体的に説明する。Next, the operation or operation method of the above-mentioned deposited film forming apparatus will be specifically explained.

まず、排気ボンｆ１４３を起動し、排気パルプ１４２を
開けて反応槽１０１ｆｔ排気し、いったん系内を充分な
高真空に保つ。次に、成膜用ガスが充填されたボンベ１
１１の開閉パルプ１１２を開き、減圧器１１３ｔ−通じ
て所定の値に減圧したのチ、成膜用ガスをマスフローコ
ントローラー１１４を通じて所定のガス流量に設定し、
ガス放出口１０２から反応槽１０１内に導入する。この
とき、成膜用ガスは一種類であってもよいし、また複数
の原料ガス、あるいは希釈ガス、ドーピングガス等をた
とえば？ンベ１２１尋の複数のボンベから供給し、ボン
ベ１１１からのガスと混合したのち反応槽１０１に導入
してもよい。こうして反応槽１０１内に所定の流量のガ
スを導入したのち、真空計１０６を見ながら排気パルプ
１４２の開閉度を調節して反応槽１０１内の圧力が所定
の値となるようにする。反応槽１０１内の圧力が所定の
圧力となったら、高周波電源１０５を用い、電極１０３
に高周波を与えて反応槽１０１内に高周波グロー放電を
生起せしめ、ヒーター１０７により所定の温度に加熱さ
れた基板１０４上に堆積膜を形成する。First, the exhaust bomb f143 is started, the exhaust pulp 142 is opened, and 101 ft of the reaction tank is evacuated, and the inside of the system is once maintained at a sufficiently high vacuum. Next, cylinder 1 filled with film-forming gas
The opening/closing pulp 112 of No. 11 is opened and the pressure is reduced to a predetermined value through a pressure reducer 113t, and the film forming gas is set at a predetermined gas flow rate through a mass flow controller 114.
The gas is introduced into the reaction tank 101 through the gas discharge port 102. At this time, one type of film-forming gas may be used, or multiple source gases, dilution gas, doping gas, etc. may be used, for example. The gas may be supplied from a plurality of 121-fathom gas cylinders, mixed with the gas from the cylinder 111, and then introduced into the reaction tank 101. After a predetermined flow rate of gas is introduced into the reaction tank 101 in this way, the degree of opening and closing of the exhaust pulp 142 is adjusted while watching the vacuum gauge 106 so that the pressure inside the reaction tank 101 becomes a predetermined value. When the pressure inside the reaction tank 101 reaches a predetermined pressure, the electrode 103 is
A high frequency wave is applied to generate a high frequency glow discharge in the reaction chamber 101, and a deposited film is formed on the substrate 104 heated to a predetermined temperature by the heater 107.

堆積膜形成開始と同時に開閉バルブ１３２ｔ−開け、少
なくともＣ１Ｆ、を含むガスの充填されたボンベ−１３
１カラ減圧器１３３．マスフローコントローラー１３４
を通して所定流量の、少なくともＣｔＦ、を含むガスを
排気管１４１に供給する。所望の厚さの堆積膜が形成さ
れた後に、成膜用ガス並びに少なくともＣＬＦ、を含む
ガスの供給を止め、系内をパージしてから反応槽１０１
をリークさせ、基板１０４を取出す。堆積膜形成中に排
気管１４１に供給され九少なくともＣ１Ｆ、を含むガス
は、排気管１４１に付着している反応生成物に作用し、
それを気相に戻し、さらには反応槽１０１から流入して
くる反応生成物の元になる前駆体を単体のシリコン系化
合物の気体となし、排気ポンプ１４３から排気する。Simultaneously with the start of deposited film formation, the opening/closing valve 132t is opened, and the cylinder 13 filled with a gas containing at least C1F is opened.
1 color pressure reducer 133. Mass flow controller 134
A predetermined flow rate of gas containing at least CtF is supplied to the exhaust pipe 141 through the exhaust pipe 141 . After a deposited film of a desired thickness is formed, the supply of the film-forming gas and the gas containing at least CLF is stopped, the system is purged, and then the reaction tank 101 is
is leaked and the substrate 104 is taken out. During the formation of the deposited film, the gas containing at least C1F supplied to the exhaust pipe 141 acts on the reaction products adhering to the exhaust pipe 141,
It is returned to the gas phase, and furthermore, the precursor that is the source of the reaction product flowing in from the reaction tank 101 is converted into a gas of a single silicon-based compound, and the gas is exhausted from the exhaust pump 143.

以上で明らかな如く、堆積膜形成時と同時に排気管１４
１に少なくともＣｌＦ３を含むガスを供給することによ
って、排気管内壁にはポリシラン等の反応生成物が付着
することなく、反応［１０１内の圧力は終始一定に保た
れ、基板１０４上には安定した品質と特性をもつ堆積膜
を形成することが可能となる。As is clear from the above, at the same time as the deposited film is formed, the exhaust pipe 14
By supplying a gas containing at least ClF3 to 101, reaction products such as polysilane do not adhere to the inner wall of the exhaust pipe, and the pressure inside 101 is kept constant from beginning to end, resulting in a stable state on the substrate 104. It becomes possible to form a deposited film with quality and properties.

なお、上記具体例では堆積膜形成用原料ガスへのエネル
ギー供給手段としてＲ，Ｆ、グロー放電を用いた例につ
いて説明したが１本発明はこれに限定されず、原料ガス
へのエネルギー供給手段としてマイクロ波グロー放電法
、　Ｄ、Ｃ，グロー放電法、光ｃＶＤ法、熱ＣＶＤ法等
を用いた場合において本適用可能である。In the above specific example, an example was explained in which R, F, and glow discharge were used as a means for supplying energy to the raw material gas for forming a deposited film, but the present invention is not limited thereto, and This method can be applied to cases where a microwave glow discharge method, a D, C, glow discharge method, a photo CVD method, a thermal CVD method, etc. are used.

また１本発明に用いる原料ガスとしてはシリコン系半導
体、たとえばシリコン膜、シリコンダルマニウム膜、シ
リコンカーバイド膜などの構成要素となるものであれば
とくに制限はない。たとえばＳｉＨ４゜Ｓ　ｌ　２Ｈ６
＋　８１　Ｆ４　＋　Ｓ　ｌ　２Ｆ６　＋ＧｅＨ４、Ｇ
ｅＦ４　、ＣＨ４、Ｃ２Ｈ２ＩＮ２＋ＮＨ３。The raw material gas used in the present invention is not particularly limited as long as it is a constituent element of silicon-based semiconductors, such as silicon films, silicon dalmanium films, and silicon carbide films. For example, SiH4゜S l 2H6
+ 81 F4 + S l 2F6 + GeH4,G
eF4, CH4, C2H2IN2+NH3.

０２、Ｎｏ等が挙げられ、希釈ガスとしてはＨ２、Ａｒ
　＋Ｈｅ等を用いることができ、また膜へのドーピング
を行なう場合にはドーピングがスとしてたとえばＢ２Ｈ
６ｅ　ＢＦ３　、　ＰＨ３，ＰＦ５　、　ＰＦ５　、　
Ｎ２等が挙げられ、以上を単体で用いてもよいし、目的
に応じて２種類以上のガスを混合して用いてもよい。02, No, etc., and diluent gases include H2, Ar
+He, etc. can be used, and when doping the film, for example, B2H can be used as a doping source.
6e BF3, PH3,PF5, PF5,
Examples include N2, and any of the above gases may be used alone, or two or more types of gases may be mixed and used depending on the purpose.

また、少なくともｃｚ、ｐ、を含むガスとしてはＣ１Ｆ
　３ガス単体を用いてもよいし５反応速度の制御、排気
・管内の圧力制御のためにたとえばＨ・、　Ａｒ等で希
釈して用いてもよい。Further, as a gas containing at least cz, p, C1F
The three gases may be used alone, or they may be diluted with, for example, H., Ar, etc. in order to control the reaction rate and the pressure in the exhaust and pipes.

さらに本発明に用いる基板としては特に制限されるもの
ではなく、目的に応じて適宜選択される。Further, the substrate used in the present invention is not particularly limited, and may be appropriately selected depending on the purpose.

九とえば導電性基板としてはＡｔ、　Ｉｓ　、　Ｆ・等
の導電性材料あるいは非導電性基板上に導電性薄膜を設
けた材料が挙げられ、また非導電性基板としてはガラス
、石英、セラミックス等が挙げられ、以上の材料を目的
に応じて平板状、円筒状等に加工して用いることができ
る。また、基板の温度も特に制限されるものではないが
、良好な特性をもつ膜を形成するため、好ましくは１０
０〜５００℃、より好ましくは２００〜３５０℃とする
のが適当である。For example, conductive substrates include conductive materials such as At, Is, F, etc., or materials in which a conductive thin film is provided on a non-conductive substrate, and non-conductive substrates include glass, quartz, ceramics, etc. The above materials can be processed into a flat plate shape, a cylindrical shape, etc. depending on the purpose. Further, the temperature of the substrate is not particularly limited, but in order to form a film with good characteristics, it is preferably 10
A suitable temperature is 0 to 500°C, more preferably 200 to 350°C.

さらに本発明では少なくともｃｔｐ、を含むガスの供給
口は、堆積室と排気管の付根の部分に位置してもよい。Furthermore, in the present invention, the supply port for the gas containing at least CTP may be located at the base of the deposition chamber and the exhaust pipe.

以下、実施例に基づいて本発明をさらに詳細に説明する
が、本発明はそれに限定されるものではない。Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto.

〔実施例〕〔Example〕

実施例１．比較例１：原料ガスへのエネルギー供給手段として高周波（Ｒ，Ｆ
）グロー放電プラズマを用いる第１図の装置を使用する
本発明の堆積膜形成時と、排気管１４１にガス供給口を
有しないこと以外は第１図と同構成の装置を用いる従来
の堆積膜形成法とによ〕、それぞれ第１表に示す条件で
先述した手順に従ってコーニングｔｒ１７０５９ガラス
基板上にシリコン系堆積膜の形成を行なった。形成した
堆積膜は非・晶質シリコン膜（ａ−８１）、非晶質シリ
コンナイトライド膜（ａ−８ｉＮ）、非晶質酸化窒素シ
リコン膜（ａ−８１ＯＮ）　、非晶質シリコンゲルマニ
ウム膜（ａ−８’ＩＧｅ）である。堆積膜形成中は本発
明方法および従来法ともに排気バルブの開閉による堆積
室内の圧力制御は行なわず、膜形成後の排気管内壁への
粉末堆積の状態を目視で観察した。又、得られた膜につ
いて、厚みの測定ならびに膜にクシ形の電極を蒸着し、
電気的特性としてσ、（明電気伝導度）、σｄ（暗電気
伝導度）をそれぞれ測定し、これらの比ｅＩｐ／σｄに
よシ光導電性を有する膜としての評価を行°逓りた。膜
形成及び評価は各々１０回行ない、バラツキの上限と下
限を示した。以上の結果を第２表に示す。第２表に明ら
かなように、ａ　−８１Ｍ。Example 1. Comparative Example 1: High frequency (R, F
) When forming the deposited film of the present invention using the apparatus shown in FIG. 1 using glow discharge plasma, and when forming a conventional deposited film using the apparatus having the same configuration as shown in FIG. 1 except that the exhaust pipe 141 does not have a gas supply port. A silicon-based deposited film was formed on a Corning TR17059 glass substrate according to the procedure described above under the conditions shown in Table 1. The deposited films formed were amorphous silicon film (a-81), amorphous silicon nitride film (a-8iN), amorphous nitrogen oxide silicon film (a-81ON), and amorphous silicon germanium film (a-81ON). a-8'IGe). During the formation of the deposited film, in both the method of the present invention and the conventional method, the pressure inside the deposition chamber was not controlled by opening and closing the exhaust valve, and the state of powder deposition on the inner wall of the exhaust pipe after the film was formed was visually observed. In addition, the thickness of the obtained film was measured, and a comb-shaped electrode was deposited on the film.
As electrical properties, σ, (bright electrical conductivity), and σd (dark electrical conductivity) were measured, and the film was evaluated as having photoconductivity based on the ratio eIp/σd. Film formation and evaluation were performed 10 times each, and the upper and lower limits of variation were shown. The above results are shown in Table 2. As evident in Table 2, a-81M.

ａ　−ＳＩＣ膜、ａ−８ｉＯＮ膜、　ａ−８ＩＧｅ膜い
づれの堆積膜形成時においても、排気管内壁の被膜及び
粉末の付着はなく、又長時間の膜堆積時にも内圧の変動
は極めて少なく、さらに得られた膜の厚さ、電気的特性
ともに°従来例に比し極めて安定していた。During the formation of the a-SIC film, the a-8iON film, and the a-8IGe film, there was no coating or powder adhesion to the inner wall of the exhaust pipe, and even during long-term film deposition, there was very little variation in the internal pressure. Furthermore, both the thickness and electrical properties of the obtained film were extremely stable compared to conventional examples.

実施例２．比較例２：ｇ１図における反応槽１０１に替えて基板の回転装置を
備えた同軸円筒型反応槽を用い、基板として円筒状アル
ミニウム基板（外径８０龍、長さ３５８順）を用いて、
本発明の堆積膜形成法により、光源として半導体レーザ
ーを用いた榛写機に搭載する電子写真用光受容部材の形
成を行なった。Example 2. Comparative Example 2: A coaxial cylindrical reaction tank equipped with a substrate rotation device was used instead of the reaction tank 101 in Fig. g1, and a cylindrical aluminum substrate (outer diameter 80 mm, length 358 mm) was used as the substrate.
By the deposited film forming method of the present invention, a light-receiving member for electrophotography to be mounted on a photographic camera using a semiconductor laser as a light source was formed.

その製造条件を第３表に示す、電子写真用光受容部材の
形成は基板側から長波長光吸収層、電荷注入阻止層、光
導を層、表面層の順に行なった。得られた電子写真用光
受容部材を複写機（商品名ＮＤ−９３３０、キャノン（
株）製）に搭載し、電子写真特性として＋６．５　ｋＶ
のコロナ放電による受容電。The manufacturing conditions are shown in Table 3. The electrophotographic light receiving member was formed in the following order from the substrate side: a long wavelength light absorbing layer, a charge injection blocking layer, a light guide layer, and a surface layer. The obtained light-receiving member for electrophotography was transferred to a copying machine (product name: ND-9330, Canon (
(manufactured by Co., Ltd.), and has +6.5 kV as an electrophotographic characteristic.
Received charge due to corona discharge.

位ならびに波長７９０朋のレーザー光源による半減露光
量による評価を行なりた。電子写真用光受容部材の形成
と評価は１０回行ない、又比較のために第３表に示した
製造条件においてＣｔＶ　、を含むガスを流さずに形成
した電子写真用光受容部材の評価も併わせて行ない、各
々について上限と下限を示した。その結果を第４表に示
す。Evaluations were made based on the light intensity and half-reduced exposure using a laser light source with a wavelength of 790 mm. The electrophotographic light receiving member was formed and evaluated 10 times, and for comparison, an electrophotographic light receiving member formed under the manufacturing conditions shown in Table 3 without flowing a gas containing CtV was also evaluated. The upper and lower limits were shown for each test. The results are shown in Table 4.

第４表に明らかなように、本発明の堆積膜形成法で形成
された電子写真光受容部材は、従来の堆積膜形成法で形
成されたそれに比べて受容電位、半減露光量のバラツキ
が少なく、鮮明な画像が得られ、電子写真特性が極めて
安定していた。又、膜形成時においては、排気管の被膜
及び粉末の付着がなく、且つ内圧変動も極めて少なく、
本発明の効果が顕著であることが確認された。As is clear from Table 4, the electrophotographic light-receiving member formed by the deposited film forming method of the present invention has less variation in acceptance potential and half-decrease exposure amount than those formed by the conventional deposited film forming method. , clear images were obtained, and the electrophotographic characteristics were extremely stable. In addition, during film formation, there is no coating or powder adhering to the exhaust pipe, and internal pressure fluctuations are extremely small.
It was confirmed that the effects of the present invention are significant.

実施例３．比較例３第、１図に示す装置を用いて本発明の堆積膜形成法によ
りアモルファスシリコン太陽電池を製造した。基板には
透明電極としてＩＴＯを蒸着した７０５９ガラス板（１
α×１眞）を用い、基板側からＰ型アモルファスシリコ
フＭ　（Ｐ型ａ−８１）、を型アモルファスシリコンＩ
Ｉ（ｉ型ａ−８１）、ｎ型アモルファスシリコン７１（
ｎ型ａ−８ｌ）の順に層形成を行ない、ｎ型ａ−８ｉ層
上に金属電極を蒸着した。その製造条件を第５表に示す
。Example 3. Comparative Example 3 An amorphous silicon solar cell was manufactured by the deposited film forming method of the present invention using the apparatus shown in FIG. The substrate is a 7059 glass plate (1
P type amorphous silicon M (P type a-81) and type amorphous silicon I from the substrate side
I (i type a-81), n type amorphous silicon 71 (
Layers were formed in the order of n-type a-8l), and a metal electrode was deposited on the n-type a-8i layer. The manufacturing conditions are shown in Table 5.

得られた太陽電池の特性をＡＭＩ光照射の下で効率（η
）、フィル・ファクター（Ｆ、Ｆ　）により評価□した
。太陽電池の形成と評価は３０回行ない、又比較のため
第５表の製造条件でＣｔＦ３ガスを流さずに゛形成した
太陽電池の評価も併わせて行ない、６各について上限と
下限を示した。その結果を第６表に示す。The characteristics of the obtained solar cell were determined by the efficiency (η
), and the fill factor (F, F ) was evaluated. The solar cells were formed and evaluated 30 times, and for comparison, solar cells formed under the manufacturing conditions shown in Table 5 without flowing CtF3 gas were also evaluated, and the upper and lower limits for each of the 6 conditions were shown. . The results are shown in Table 6.

第６表に明らかなように、本発明方法で製造した太陽電
池は、従来方法で製造したそれに比べ、効率（ダ）、フ
ィル・ファクタ（Ｆ、Ｆ　）のバラツキが少なく、太陽
電池としての特性が安定していた。又、本発明の実施例
においては排気管への被膜及び粉末の付着のないことが
確認され、且つ膜堆積時の圧力変動が極めて少なく、本
発明の効果が顕著である。As is clear from Table 6, the solar cells manufactured by the method of the present invention have less variation in efficiency (Da) and fill factor (F, F) than those manufactured by the conventional method, and have excellent characteristics as solar cells. was stable. Further, in the examples of the present invention, it was confirmed that there was no adhesion of film or powder to the exhaust pipe, and the pressure fluctuation during film deposition was extremely small, so the effects of the present invention are remarkable.

以上、Ｒ，Ｆグロー放電を用いた湯合の本発明の実施例
を示したが、原料ガス分解法としてＲ，Ｆグロー放電に
限らず、マイクロ波グロー放電、Ｄ、Ｃグロー放電、さ
らには光（至）法、熱（至）法なども採用できることは
言うまでもない。The embodiments of the present invention using R, F glow discharge have been shown above, but the raw material gas decomposition method is not limited to R, F glow discharge, but also includes microwave glow discharge, D, C glow discharge, and more. It goes without saying that light (to) methods, heat (to) methods, etc. can also be adopted.

Ｃ発明の効果〕以上で明らかなように、本発明の堆積膜形成法によれば
、堆積膜形成時に排気路内壁に付着する反応生成物の除
去を堆積膜形成と同時だ行うことができる。C. Effects of the Invention] As is clear from the above, according to the method for forming a deposited film of the present invention, the reaction products that adhere to the inner wall of the exhaust passage during the formation of the deposited film can be removed simultaneously with the formation of the deposited film.

すなわち、堆積膜形成時の堆積室内の圧力変動を抑える
ことができ、高効率だ品質及び特性の安定した堆積膜を
形成することができる。That is, it is possible to suppress pressure fluctuations in the deposition chamber during the formation of a deposited film, and it is possible to form a deposited film with high efficiency and stable quality and properties.

また、排気系のクリーニングのためのエネルギー供給手
段を必要とせず、低コストで且つ品質及び特性の安定し
た堆積膜を形成することができる。Furthermore, there is no need for energy supply means for cleaning the exhaust system, and a deposited film with stable quality and properties can be formed at low cost.

さらに、排気系に原料ガスの重合体が蓄積しないため、
排気系のメインテナンスの際に該重合体の、空気との接
触によって発生することがある急激な酸化による事故も
、未然に防止することができる。Furthermore, since polymers of raw material gas do not accumulate in the exhaust system,
Accidents due to rapid oxidation that may occur due to contact of the polymer with air during exhaust system maintenance can also be prevented.

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

第１図は、Ｒ，Ｆグロー放電を周込て本発明方法を実施
する際用いる堆積膜形成製ａＴの一例を示す模式的構成
図である。１０１・・・反応槽、１０２・・・原料ガス放出口、１
０３・・・電極、１０４・・・基板、１０５・・・高周
波電源、１０６・・・真空計、１０７・・・ヒーター、
１０８・・・ヒーター用電源、１１１，１２１・・・原
料ガスｇンペ、１３１・・・Ｃ１Ｆ、含有ガスボンベ、
１１２゜１２２．１３２・・・開閉バルブ、１１３，１
２３゜１３３・・・減圧器、１１４，１２４，１３４・
・・マスフローコントローラー、１４１・・・排’Ａ’
Ｑ、１４２・・・排気パルプ、１４３・・・排気ポンプ
。代理人　弁理士　山　下　穣　平手続補正書昭和６３年　７月２２日FIG. 1 is a schematic diagram showing an example of a deposited film forming aT used when carrying out the method of the present invention including R and F glow discharges. 101... Reaction tank, 102... Raw material gas discharge port, 1
03... Electrode, 104... Substrate, 105... High frequency power supply, 106... Vacuum gauge, 107... Heater,
108... Power source for heater, 111, 121... Raw material gas pump, 131... C1F, containing gas cylinder,
112゜122.132...Opening/closing valve, 113,1
23゜133...pressure reducer, 114,124,134・
...Mass flow controller, 141...Exhaust 'A'
Q, 142...Exhaust pulp, 143...Exhaust pump. Agent Patent Attorney Jo Yamashita Hei Proceedings Amendment July 22, 1988

Claims (1)

Translated fromJapanese

【特許請求の範囲】[Claims]　気相法により基体上に堆積膜を形成するための堆積室
と該室内を排気するための排気系とを備えた堆積膜形成
装置を用いる堆積膜形成法において、堆積膜形成時に、
前記排気系の排気路にＣｌＦ＿３を供給することを特徴
とする堆積膜形成法。In a deposited film forming method using a deposited film forming apparatus equipped with a deposition chamber for forming a deposited film on a substrate by a vapor phase method and an exhaust system for exhausting the interior of the chamber, when forming the deposited film,
A deposited film forming method characterized by supplying ClF_3 to the exhaust path of the exhaust system.