JP3710171B2 - Method for forming electrophotographic photosensitive member - Google Patents

Description

得られた電子写真感光体は次の方法で評価した。
【００９８】
各々の感光体について電子写真装置（キヤノン社製ＮＰ６０６０を実験用に改造したもの）にセットして、初期の帯電能、残留電位等の電子写真特性を次のように評価した。
【００９９】
帯電能 …電子写真用感光体を実験装置に設置し、帯電器に＋６ｋＶの高電圧を印加しコロナ帯電を行ない、表面電位計により電子写真感光体の暗部表面電位を測定する。
【０１００】
帯電ムラ…電子写真感光体を電子写真装置に設置し、帯電器に＋６ｋＶの高電圧を印加しコロナ帯電を行ない、表面電位計により電子写真感光体の暗部表面電位を現像位置で測定する。電子写真感光体の軸方向に５点測定し、このときの電位ムラを評価する。
【０１０１】
感度ムラ…電子写真感光体を、一定の暗部表面電位に帯電させる。そして直ちにフィルターを用いて６００ｎｍ以上の波長域の光を除いたハロゲンランプ光を照射し、電子写真感光体の明部表面電位が所定の値になるように光量を調整する。このときに必要な光量をハロゲンランプ光源の点灯電圧から換算する。この手順で電子写真感光体の軸方向に５点感度を測定し、このときの感度ムラを評価する。
【０１０２】
残留電位…電子写真感光体を、一定の暗部表面電位に帯電させる。そして直ちに一定光量の比較的強い光を照射する。光像はハロゲンランプ光源を用い、フィルターを用いて６００ｎｍ以上の波長域の光を除いた光を照射した。この時表面電位計により電子写真感光体の明部表面電位を測定する。
【０１０３】
濃度ムラ…電子写真感光体の表面電位を現像位置において所定の暗部表面電位に帯電させる。そして直ちにハロゲンランプを光源とし、フィルターを用いて６００ｎｍ以上の波長域の光を除いた光を照射し、表面電位が５０Ｖになる時の光量を測定する。次に前記と同様に所定の表面電位に帯電させた後に前記光量の１／２光量を照射し、現像器により現像を行う。この時の画像濃度を電子写真感光体の軸方向に５点測定し、評価した。但し、画像濃度の測定は、画像濃度計：Ｍａｃｂｅｔｈ ＲＤ９１４を用いた。
【０１０４】
画像流れ…高温高湿環境（気温：３０℃、湿度：８０％）下で、画像形成時の原稿として、図４に示す黒色部と白色部とが一定の幅ａで並んだテストチャートを用意し、線幅ａを狭めていった時に、複写画像上において再現し解像し得る最小の線幅ａにより評価を行った。すなわち、テストチャートにおける線幅ａを小さくしていった時に、ある線幅ａ以下になると、画像上の隣り合う黒色部の輪郭の画像流れによる微小なボケが重なり合い、事実上解像不可となってしまう。そのときの線幅ａの数値を、画像流れ程度を表すものとして評価した。
【０１０５】
白ポチ …キヤノン製全面黒チャート（部品番号：ＦＹ９−９０７３）を原稿台に置きコピーしたときに得られたコピー画像の同一面積内にある直径０．２ｍｍ以上の白ポチの数によって評価した。評価の表示区分は次のとおり。
それぞれについて、
◎ 非常に良好
〇 良好
△ 従来レベルで実用上問題無し
× 実用上問題有り
膜の密着性試験…１００ｇの鉄球を５０ｃｍの高さから落下させて電子写真感光体に衝突させた。このとき生じた打痕を詳細に観察し、ａ−Ｓｉ膜と基体の密着性を評価した。
【０１０６】
◎ 打痕の回りの膜に全くひび割や膜剥がれはなく、非常に良好
〇 僅かにひび割れはあるが膜剥がれはなく、良好
△ ひび割れはあるが膜剥がれはなく、実用上問題無し
× 打痕の回りの膜に膜剥がれが発生し、実用上問題有り
成膜時間…比較例１のトータルの成膜時間を基準とした時の成膜時間を評価した。
【０１０７】
◎ 比較例１より成膜時間が10％以上短い
〇 比較例１より成膜時間が10％程度短い
△ 比較例１とほぼ同等の時間
× 比較例１より成膜時間が長い
以上の評価結果を、同様の方法で評価した後述する参考例２、実施例１〜４および比較例１〜２の結果とともに、表２にまとめて示す。
【０１０８】
参考例２
使用発振周波数を変えた以外は参考例１と同様にして、電子写真用感光体を作成した。下部阻止層〜光導電層を発振周波数13.56ＭＨzの高周波電源を使用して成膜を行った後、一旦放電を切り、高周波電源を105ＭＨzのものに置き換えて表面保護層を成膜した。
実施例１
使用発振周波数を変えた以外は参考例１と同様にして、電子写真用感光体を作成した。下部阻止層では発振周波数13.56ＭＨzの高周波電源を使用して成膜を行った後、一旦放電を切り、高周波電源を105ＭＨzのものに置き換えて光導電層を成膜した。更に光導電層の成膜終了後に一旦放電を切り、再び電源を13.56ＭＨzに戻して表面保護層を成膜した。
実施例２
使用発振周波数を変えた以外は参考例１と同様にして、電子写真用感光体を作成した。下部阻止層では発振周波数105ＭＨzの高周波電源を使用して成膜を行った後、一旦放電を切り、高周波電源を13.56ＭＨzのものに置き換えて光導電層を成膜した。更に光導電層の成膜終了後に一旦放電を切り、再び電源を105ＭＨzに戻して表面保護層を成膜した。
実施例３
図２に示した堆積膜形成装置においてアルミニューム製の円筒状基体の表１の製造条件(内圧を除く)に従ってa-Ｓi膜を形成し、電子写真用感光体を作成した。本実施例では下部阻止層〜光導電層を発振周波数で使用する高周波電源の発振周波数は80ＭＨzとし、内圧を0.05Ｔorrで成膜し、その他の層領域では10ＭＨzの高周波電源を用いて内圧0.5Ｔorrで成膜を行った。
実施例４
使用発振周波数を変えた以外は実施例３と同様にして、電子写真用感光体を作成した。光導電層〜表面層で使用する高周波電源の発振周波数は60ＭＨzとし、内圧を0.04Ｔorrで成膜し、下部阻止層では15ＭＨzの高周波電源を用いて内圧0.45Ｔorrで成膜を行った。
比較例１
図１に示した堆積膜形成装置において発振周波数13.56ＭＨzの高周波電源を設置し、アルミニューム製の円筒状基体にa-Ｓi膜を形成し、電子写真用感光体を作成した。本比較例では表１の製造条件に従って、下部阻止層、光導電層、および表面保護層すべてを発振周波数13.56ＭＨzの高周波電源で成膜を行った。
比較例２
図２に示した堆積膜形成装置において発振周波数13.56ＭＨzの高周波電源を設置し、アルミニューム製の円筒状基体にa-Ｓｉ膜を形成し、電子写真用感光体を作成した。本比較例では表１の製造条件に従って、下部阻止層、光導電層、および表面保護層すべてを発振周波数13.56ＭＨzの高周波電源で成膜を行った。
【０１０９】
【表２】

【０１１０】
以上の結果、本発明の電子写真感光体は比較例１、２に示した従来の感光体に比べてすべての評価において非常に良好な特性を示すことが判明し、本発明の優位性が明らかとなった。
【０１１１】
参考例３
参考例１と同様の堆積膜形成装置および手順でアルミニューム製の円筒状基体に表１の製造条件に従ってa-Ｓi膜を形成し、電子写真用感光体を作成した。但し、本実施例では下部阻止層で使用する高周波の発振周波数を105ＭＨzから200ＭＨzに変更した。成膜時の内圧は参考例１と同様に0.02Ｔorrである。こうして作成した電子写真用感光体を参考例１、２及び実施例１〜４と同様の手順で評価を行ったところ、参考例１と同様の良好な結果が得られた。
参考例４
参考例２と同様の堆積膜形成装置、および手順でアルミニューム製の円筒状基体に表１の製造条件に従ってa-Ｓi膜を形成し、電子写真用感光体を作成した。但し、本実施例では表面保護層で使用する高周波の発振周波数を105ＭＨzから300ＭＨzに変更した。成膜時の内圧は実施例２と同様に0.03Ｔorrである。こうして作成した電子写真用感光体を参考例１、２及び実施例１〜４と同様の手順で評価を行ったところ、参考例２と同様の良好な結果が得られた。
実施例５
実施例１と同様の堆積膜形成装置および手順でアルミニューム製の円筒状基体に表１の製造条件に従ってa-Ｓi膜を形成し、電子写真用感光体を作成した。但し、本実施例では光導電層で使用する高周波の発振周波数を105ＭＨzから50ＭＨzに変更した。成膜時の内圧は実施例１と同様に0.03Ｔorrである。こうして作成した電子写真用感光体を参考例１、２及び実施例１〜４と同様の手順で評価を行ったところ、実施例１と同様の良好な結果が得られた。
【０１１２】
【発明の効果】
以上詳細に説明したように少なくともシリコン原子を母材とする非結晶質材料から成る電子写真感光体を製造する方法において、発振周波数が２０ＭＨｚ未満の高周波電力により励起されたグロー放電により堆積される層と、発振周波数が５０ＭＨｚ以上、４５０ＭＨｚ以下の高周波電力により励起されたグロー放電により堆積される層とが混在するように形成させることによって、高速の処理速度で比較的大面積の基体をプラズマ処理でき、帯電性能が高く、画像濃度が濃く、製造時間が短く低コストであり、高温、高湿度の環境で用いても画像品質が低下せず、更に製造工程で多少の条件変動があっても膜剥がれ等のトラブルが発生しない、安定で、再現性が良く、製造工程管理が容易な電子写真感光体を提供することができる。
【図面の簡単な説明】
【図１】本発明の電子写真感光体の形成方法に使用する装置の一例を示す模式図である。
【図２】本発明の電子写真感光体の形成方法に使用する装置の他の例を示す模式図である。
【図３】従来の電子写真感光体の形成方法に使用する装置の一例を示す模式図である。
【図４】本発明の電子写真感光体の画像流れ試験用チャートの模式図である。
【符号の説明】
１０１、２０１、３０１ 堆積室
１０２、２０２、３０２ 被成膜基体を兼ねる第１の電極
１０３、２０３、３０３ 加熱用ヒーター
１０４、３０４ メインバルブ
１０５、２０５、３０５ 原料ガス放出パイプ
１０６、２０６、３０６ 第２の電極
１０７、２０７、３０７ 補助基体
１０８、３０８ 排気装置
１０９、２０９、３０９ 原料ガス導入バルブ
１１０、２１０、３１０ 圧力ゲージ
１１１、２１１、３１１ 整合器
１１２、２１２、３１２ 高周波電源
１１３、３１３ 絶縁材
１１４、３１４ 絶縁された炉壁
１１５、２１５、３１５ 排気口[0001]
BACKGROUND OF THE INVENTION
The present invention is a plasma capable of satisfactorily forming crystalline and non-single crystalline functional deposition films useful for electrophotographic photoreceptor devices as semiconductor devices, image input line sensors, imaging devices, photovoltaic devices and the like. The present invention relates to a CVD apparatus, a semiconductor device, a sputtering apparatus capable of suitably forming an insulating film as an optical element, a metal wiring, or the like, or a plasma processing apparatus such as an etching apparatus such as a semiconductor device, and a processing method thereof. The present invention relates to a plasma processing method for performing a laminating process on a substrate using as an excitation source, and more particularly to a plasma processing method using a high frequency of 450 MHz or less.
[0002]
[Prior art]
Various apparatuses and methods are applied to the plasma processing used in the manufacture of semiconductors according to the respective applications. For example, formation of oxide film, nitride film, amorphous silicon-based semiconductor film using plasma CVD apparatus or plasma CVD method, formation of metal wiring film using sputtering apparatus or sputtering method, fine processing using etching apparatus or etching method Devices and methods that make use of their characteristics are used in various technologies. Furthermore, in recent years, demands for improving film quality and processing capacity have increased, and various ideas have been studied. In particular, a plasma process using high-frequency power is widely used because of its various advantages such as high discharge stability and the ability to be used for forming insulating materials such as oxide films and nitride films.
[0003]
Conventionally, in a plasma process such as plasma CVD, an oscillation frequency of a discharge high-frequency power source is 20 MHz or less, and generally 13.56 MHz.
[0004]
An example of a plasma CVD apparatus generally used for the conventional deposited film formation is shown in FIG. The plasma CVD apparatus shown in this figure is a film forming apparatus suitable for forming an amorphous silicon film (hereinafter referred to as a-Si film) on a cylindrical electrophotographic photosensitive member substrate. Hereinafter, a method for forming an a-Si film using this apparatus will be described.
[0005]
A cylindrical second electrode 306 that also serves as an inner wall of the deposition chamber 301 that can be depressurized, and a first electrode 302 that also serves as a film formation substrate (electrophotographic photosensitive member substrate) are disposed as a counter electrode. An auxiliary base 307 is attached to the first electrode 302 and forms a part of the first electrode. In general, the dimension of the second electrode 306 in the cylindrical axis direction is set to be approximately the same as the length of the first electrode 302 and the auxiliary base 307 in the cylindrical axis direction. The first electrode 302 is heated from the inside by an internal heater 303. The high frequency power supply 312 is connected to the second electrode 306 through the matching circuit 311. 315 is an exhaust port, 304 is a main valve, 310 is a pressure gauge, 305 is a gas discharge pipe, and 309 is a source gas introduction valve.
[0006]
A deposition target substrate 302 that also serves as a first electrode is installed in the deposition chamber 301, the main valve 304 is opened, and the deposition chamber 301 is temporarily evacuated through the exhaust port 315. Thereafter, the raw material gas inlet 309 is opened, an inert gas is introduced, and the flow rate is adjusted to a predetermined pressure. The heating heater 303 is energized to heat the substrate to be deposited to a desired temperature of 100 to 400 ° C. Thereafter, a raw material gas for film formation, for example, a material gas such as silane gas, disilane gas, methane gas, and ethane gas, and a doping gas such as diborane gas and phosphine gas are introduced through a raw material gas introduction valve 309, and several hundred mTorr to several Torr. Adjust pumping speed to maintain pressure.
[0007]
A high frequency power of 13.56 MHz is supplied from the high frequency power supply 312 to the second electrode 306 through the matching circuit 311 to generate a plasma discharge between the second electrode 306 and the first electrode 302, thereby supplying a source gas. By decomposing, an a-Si film is deposited on the deposition target substrate 302 that also serves as the first electrode. During this time, the first electrode is maintained at about 100 to 400 ° C. by the heater 303. If necessary, the film formation substrate may be rotated by a rotation mechanism (not shown) to improve the film thickness distribution in the circumferential direction.
[0008]
Higher performance and higher functionality are being pursued in current copying machines using electrophotographic photosensitive members. One of the pursued performance goals is to improve copy speed. The higher the copy speed, the shorter the time that can be spent for charging, and the charged potential of the photoreceptor tends to decrease. In addition, multi-color copying can be cited as one of the advanced functions. In this case, since it is necessary to install a plurality of developing units in the copying machine, the distance from the charging unit to the developing unit tends to increase. In addition, the surface potential of the photoreceptor tends to be attenuated, and the charged potential of the photoreceptor in the developing device tends to decrease. As described above, further improvement in charging ability is desired in the electrophotographic photoreceptor using the a-Si film.
[0009]
The deposition rate for obtaining an a-Si film satisfying the performance of the electrophotographic photosensitive member by the conventional film formation method is, for example, about 0.5 to 6 μm per hour. The body may not be able to get its properties. In general, when an a-Si film is used as an electrophotographic photosensitive member, a film thickness of at least 20 to 30 μm is necessary in order to obtain a sufficient charging ability due to the size of the dielectric constant. Therefore, it takes a long time to manufacture the electrophotographic photosensitive member, which has been a factor in increasing the manufacturing cost. For this reason, a technique for shortening the manufacturing time without deteriorating the characteristics as a photoreceptor has been desired.
[0010]
Furthermore, in the Carlson-type electrophotographic process, a step of charging the electrophotographic photosensitive member is required. In particular, an electrophotographic photosensitive member using an a-Si film is frequently used in a relatively high-speed copying machine, and thus corona. A charging process by discharge is often used. In this case, a corona product generated during charging may adhere to the surface of the photoreceptor. These deposits are easy to absorb moisture, and in high temperature and high humidity environments, corona products absorb moisture, the surface of the photoconductor becomes low resistance, the charge carrier flows laterally, and thin lines of the image are blurred (so-called image flow). May occur.
[0011]
Further, as described above, when an a-Si film is used as an electrophotographic photosensitive member, a film thickness of at least 20 to 30 μm is necessary to obtain charging ability, and such a thick film is formed. In this case, stress tends to accumulate in the film. Therefore, the adhesiveness required to overcome the stress accumulated in the thick film is required between the a-Si film and the substrate. However, if the film forming conditions are slightly shifted, this balance is lost and film peeling occurs. was there. For this reason, in the manufacture of an electrophotographic photosensitive member using an a-Si film, the yield rate may be lowered unless the process is strictly managed.
[0012]
[Problems to be solved by the invention]
The first object of the present invention is to overcome the problems of the prior art as described above, and to obtain an image having a high density and high density at the time of charging, which cannot be achieved by the conventional plasma process. It is to provide an optimum method for manufacturing a photoreceptor. A second object of the present invention is to provide an optimum method for producing a low-cost electrophotographic photosensitive member having a short production time and excellent reproducibility.
The third object of the present invention is to provide an electrophotographic photosensitive material which has high environmental resistance, does not deteriorate image quality even when used in a high temperature and high humidity environment, has a high density, and provides a clear image without fogging on a white background. Is to provide a body.
A fourth object of the present invention is to provide a method for producing an electrophotographic photosensitive member that does not cause troubles such as film peeling even if there are some fluctuations in conditions in the production process, is stable and has good reproducibility, and easy process management. It is to be.
[0013]
[Means for Solving the Problems]
  The present invention which achieves the above object is to provide a conductive cylindrical substrate in a vacuum-tight deposition chamber connected to an exhaust means and provided with a source gas supply means, and at least a gaseous source containing at least silicon atoms to a high frequency. In a production method for producing an electrophotographic photosensitive member by decomposing by glow discharge excited by electric power and depositing an amorphous material having at least a silicon atom as a base material on the cylindrical substrate,The electrophotographic photoreceptor is a blocking typeThe deposited layer on the cylindrical substrate isAt least a lower blocking layer and a photoconductive layer, the photoconductive layer being 50 MH z that's all, 450 MH z The following high frequency power is used to form layers other than the photoconductive layer. 20 MH z Form with less than high frequency powerThis is a method for forming an electrophotographic photosensitive member.
  Specifically, the electrophotographic photoreceptor has a surface protective layer, and the surface protective layer is 20 MH z It is characterized by being formed using less high frequency power.
  In addition, the present invention provides a conductive cylindrical substrate in a vacuum-tight deposition chamber connected to an exhaust means and provided with a source gas supply means, and excites a gaseous source containing at least silicon atoms with high-frequency power. In a manufacturing method for producing an electrophotographic photosensitive member by decomposing by a glow discharge and depositing an amorphous material having at least silicon atoms as a base material on the cylindrical substrate, the electrophotographic photosensitive member is a blocking type. The deposited layer on the cylindrical substrate comprises at least a lower blocking layer, a photoconductive layer, and a surface protective layer, and the lower blocking layer and the surface protective layer are 50 MH z that's all, 450 MH z The following high frequency power is used to form a layer other than the lower blocking layer and the surface protective layer. 20 MH z The electrophotographic photosensitive member is formed by using less high-frequency power.
  Furthermore, the present invention provides a conductive cylindrical substrate in a vacuum-tight deposition chamber connected to an exhaust means and provided with a source gas supply means, and excites a gaseous source containing at least silicon atoms with high-frequency power. In a manufacturing method for manufacturing an electrophotographic photosensitive member by decomposing by a glow discharge and depositing an amorphous material having at least silicon atoms as a base material on the cylindrical substrate, the electrophotographic photosensitive member is a blocking type. The deposited layer on the cylindrical substrate has a lower blocking layer, a photoconductive layer and a surface protective layer, and the lower blocking layer and the photoconductive layer are used with a high frequency power of 50 MHz or more and 450 MHz or less. And forming the surface protective layer using a high-frequency power of less than 20 MHz.It is.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The RF plasma CVD method, which is a film forming method that uses a high frequency of 20 MHz or less as the high frequency power, is a dense and hard film to be deposited, and is also suitable for forming a large area device such as an electrophotographic photosensitive member. And non-uniformity in film quality hardly occur, and is relatively suitable as a method for producing an electrophotographic photosensitive member. However, on the other hand, the major themes are not only the charging performance is insufficient, the deposition rate is low, the film formation time is long, the environment resistance is further improved, and troubles such as film peeling during production are prevented. It has become.
[0015]
Recently, a plasma CVD method using a parallel plate type plasma CVD apparatus and a high frequency power source of 50 MHz or more has been reported (Plasma Chemistry and Plasma Processing, Vol. 7, No. 3, (1987) p267-273), and discharge. The possibility of improving the deposition rate without degrading the performance of the deposited film by increasing the frequency from the conventional 13.56 MHz has been shown and has attracted attention. The report of increasing the discharge frequency is also made by sputtering, and its superiority has been widely studied in recent years.
[0016]
In these plasma CVD film formation using high frequency power of 50 MHz or more, high energy plasma can be easily generated, so that a high quality deposited film can be easily obtained, and the deposition rate can be easily improved for the same reason. Further, since ion bombardment can be reduced, the film stress can be reduced and the adhesion of the film can be improved.
[0017]
The present inventors have found that the above-mentioned problems can be solved by combining this improved plasma CVD method and the conventional RF plasma CVD method.
[0018]
That is, a layer with an electrophotographic photosensitive member deposited layer is formed with a high frequency power of 50 MHz to 450 MHz, and other layers are formed with a conventional high frequency power of 20 MHz or less, thereby exhibiting unprecedented excellent characteristics. It has been found that a photoreceptor can be obtained. Specifically, there are the following various processes.
(1) A film prepared by high frequency power of 50 MHz or more is applied to the layer region in contact with the substrate, and the other layers are deposited by high frequency power of 20 MHz or less, for example, 13.56 MHz. By this method, it is possible to produce an electrophotographic photosensitive member that is uniform in quality without uneven charging ability and does not cause film peeling during production.
(2) A film prepared by high frequency power of 50 MHz or more is applied to the outermost layer, and the layers other than the outermost surface are deposited by high frequency power of, for example, 13.56 MHz of 20 MHz or less. By this method, a dense and highly water-repellent film covers the outermost surface, and image flow hardly occurs in a high temperature and high humidity environment.
(3) A film prepared with high frequency power of 50 MHz or more is applied to the photoconductive layer, and the layers other than the photoconductive layer are deposited with high frequency power of 20 MHz or less, for example, 13.56 MHz. In this method, the deposition rate is high, the film formation time can be shortened, and the manufacturing cost can be shortened.
(4) A film prepared by high frequency power of 50 MHz or more is applied to the layer in contact with the substrate and the outermost layer, and the intermediate layer is deposited by high frequency power of 20 MHz or less, for example, 13.56 MHz. By this method, a uniform quality with no uneven charging ability, no film peeling during production, and a highly water-repellent film covers the outermost surface, and image flow is prevented in a high temperature and high humidity environment. It is possible to produce an electrophotographic photosensitive member that hardly occurs.
Hereinafter, the present invention will be described in detail with reference to the drawings.
[0019]
FIG. 1 schematically shows an example of an apparatus for carrying out the method of the present invention. A so-called coaxial type in which a second electrode is provided so as to surround a cylindrical substrate of an electrophotographic photosensitive member. This is a deposited film forming apparatus.
[0020]
In the figure, reference numeral 101 denotes a deposition chamber for forming a deposited film, and an exhaust port 115 is connected to an exhaust device 108 via a main valve 104. As the exhaust device 108, for example, a combination of a mechanical booster pump and a rotary pump, a combination of a diffusion pump and a rotary pump, or the like is preferably used. These exhaust devices may be provided with a variable conductance valve or the like as necessary. Reference numeral 109 denotes a source gas introduction valve for introducing the source gas into the deposition chamber, and introduces the source gas into the deposition chamber from a gas supply system (not shown). The source gas is discharged into the discharge space from the gas discharge pipe 105 set up in the deposition chamber. The pressure in the deposition chamber when the source gas is introduced can be monitored with the pressure gauge 110. The optimum degree of vacuum may differ between the plasma CVD method at a frequency of less than 20 MHz and the plasma CVD method at a frequency of 50 MHz to 450 MHz. In this case, the mechanical booster pump (not shown) of the exhaust device 108 is driven. An appropriate degree of vacuum may be adjusted by adjusting the frequency or separately using a variable conductance valve. Reference numeral 102 denotes a first electrode serving as a film formation substrate connected to the ground, and auxiliary substrates 107 are provided above and below the film formation substrate. Reference numeral 103 denotes a heater for heating the substrate to a predetermined temperature. In addition, although the deposition target substrate is fixed in this schematic diagram, it can be rotated by a rotating mechanism as necessary to further uniform the film thickness in the circumferential direction. Reference numeral 112 denotes a high frequency power source that generates a high frequency of 50 MHz to 450 MHz or 20 MHz or less, and the high frequency output is wired so as to be applied to the second electrode 106 via the matching circuit 111. Of course, the second electrode 106 may also serve as the inner wall of the deposition chamber 101 as shown in the figure.
[0021]
The second electrode 106 can be adjusted to an appropriate length in the axial direction so that electric power can be efficiently introduced into the deposition chamber 101 at a frequency of 20 MHz or less or a frequency of 50 MHz to 450 MHz. . This schematic diagram shows an example in which the second electrode 106 is slightly shorter than the total length of the first electrode 102 and the auxiliary base 107 using the inner wall 114 electrically insulated by the insulating material 113. .
[0022]
To switch the frequency in actual film formation, both the high-frequency power source 112 and the matching circuit 111 are replaced, or if the matching circuit has a wide matching range, the matching circuit 111 is fixed and only the high-frequency power source has a different frequency. By exchanging, the present invention can be achieved. A matching circuit having a wide matching range and a high-frequency power supply capable of changing the frequency from 20 MHz or less to 50 MHz or more can advantageously achieve the method of the present invention without replacing the matching circuit 111 and the high-frequency power supply 112. .
[0023]
FIG. 2 schematically shows an example of another apparatus for carrying out the method of the present invention, in which a cylindrical substrate such as an electrophotographic photoreceptor is placed on a concentric circle and surrounded by the substrate. This is a deposited film forming apparatus in which discharge is excited inside.
In the figure, reference numeral 201 denotes a deposition chamber for forming a deposited film, and shows a form in which a cylindrical substrate 202 that also serves as a first electrode surrounds a second electrode 206. The deposition chamber 201 has an exhaust port 215 and is connected to an exhaust device (not shown). As the exhaust device, for example, a combination of a mechanical booster pump and a rotary pump, a combination of a diffusion pump and a rotary pump, or the like is preferably used. A variable conductance valve or the like may be attached to the exhaust port 215 as necessary.
[0024]
Reference numeral 209 denotes a source gas introduction valve for introducing the source gas into the deposition chamber, and introduces the source gas into the deposition chamber from a gas supply system (not shown). The source gas is discharged from the gas discharge pipe 205 into the discharge space in the deposition chamber. The pressure in the deposition chamber when the source gas is introduced can be monitored with the pressure gauge 210. The optimum degree of vacuum may differ between the plasma CVD method at a frequency of less than 20 MHz and the plasma CVD method at a frequency of 50 MHz to 450 MHz. In this case, the drive frequency of the mechanical booster pump of the exhaust device described above is adjusted. Or, it may be adjusted to an appropriate degree of vacuum by separately using a variable conductance valve.
[0025]
Reference numeral 202 denotes a first electrode serving as a film formation substrate connected to the ground, and auxiliary substrates 207 are provided above and below the film formation substrate. Reference numeral 203 denotes a heater for heating the substrate to a predetermined temperature. The deposition target substrate 202 is rotated by a rotation mechanism so that the film thickness in the circumferential direction can be made uniform. Reference numeral 212 denotes a high frequency power source that generates a high frequency of 50 MHz to 450 MHz or 20 MHz or less, and the high frequency output is wired so as to be applied to the second electrode 206 via the matching circuit 211.
[0026]
The second electrode 206 has an optimal apparatus configuration by appropriately adjusting the axial length so that power can be efficiently introduced into the deposition chamber 201 at a frequency of 20 MHz or less or a frequency of 50 MHz to 450 MHz. Can do.
[0027]
To switch the frequency in actual film formation, both the high-frequency power supply 212 and the matching circuit 211 are replaced, or if the matching circuit has a wide matching range, the matching circuit 211 is fixed and only the high-frequency power supply has a different frequency. By exchanging, the present invention can be achieved. In addition, a matching circuit having a wide matching range and a variable high-frequency power source whose frequency is variable from 20 MHz to 50 MHz or more can advantageously achieve the method of the present invention without replacing the matching circuit 211 and the high-frequency power source 112.
[0028]
Any high frequency power source may be used as long as it is a power source that generates a frequency of less than 20 MHz and a power source that generates a frequency from 50 MHz to 450 MHz. A high-frequency power source of a type that can change the oscillation frequency, in particular, one that can be varied from a frequency of 20 MHz or less to a frequency of 50 MHz or more is preferably applied to the method of the present invention. Any power output can be suitably used as long as it can generate power suitable for the device and the prescription from 10 W to 5000 W or more.
[0029]
Furthermore, the effect of the present invention can be obtained regardless of the value of the output fluctuation rate of the high-frequency power source.
[0030]
The matching circuit used can be suitably used in any configuration as long as the high frequency power supply and the load can be matched. As a method for obtaining the alignment, an automatically adjusted method is preferable in order to avoid complications during manufacturing, but even the manually adjusted method has no influence on the effect of the present invention. There is no problem with the position where the matching circuit is arranged, so long as the matching circuit can be located anywhere. However, it is better to make the wiring inductance between the matching circuit and the second electrode as small as possible. This is desirable because it enables matching under a wide load condition.
[0031]
An example of the deposited film forming method of the present invention using the deposited film forming apparatus of FIG. 1 is performed as follows.
First, an auxiliary substrate 107 is attached to a film formation substrate (also serving as a first electrode) 102 whose surface has been mirror-finished using, for example, a lathe, and the film formation substrate 107 is attached to the heater 103 in the deposition chamber 101. insert.
[0032]
Next, the source gas introduction valve 109 is closed, the main valve 104 is opened, and the deposition chamber is once exhausted from the exhaust port 115. Then, the source gas introduction valve 109 is opened and an inert gas for heating, for example, argon is used as a source material. The gas is introduced into the deposition chamber through the gas discharge pipe 105, and the flow rate of the heating inert gas is adjusted while monitoring the pressure gauge 110 so that the deposition chamber has a desired pressure. Thereafter, a temperature controller (not shown) is operated to heat the substrate 102 with the heater 103 for heating, and when the substrate 102 is heated to a desired temperature, the source gas introduction valve 109 is closed to stop the gas flow into the deposition chamber.
[0033]
The deposition film is formed by opening the source gas introduction valve 109 and depositing a predetermined source gas such as silane gas, disilane gas, methane gas, and ethane gas, and a doping gas such as diborane gas and phosphine gas from the source gas inlet 105. The pumping speed is adjusted so that the pressure is introduced into 101 and maintained at a desired pressure of several mTorr to several Torr. As an adjustment method, a method of appropriately adjusting the opening degree of the main valve 104, a method of adjusting using an unillustrated conductance adjustment valve, or a combination of a mechanical booster pump and a rotary pump in the exhaust system is used. In some cases, there is a method of adjusting the rotational frequency of the mechanical booster pump. After the pressure is stabilized, the high-frequency power source 112 is turned on to cause glow discharge.
[0034]
At this time, high-frequency power with an oscillation frequency of less than 20 MHz is input when a certain layer is formed, and high-frequency power with an oscillation frequency of 50 MHz or more and 450 MHz or less is input when another layer is formed. Which layer is formed is appropriately selected as to whether high frequency power of less than 20 MHz or high frequency power of 50 MHz or more and 450 MHz or less is input.
[0035]
In any case, the matching circuit 111 is adjusted so that the reflected wave is minimized. The value obtained by subtracting the reflected power from the high-frequency incident power is adjusted to a desired value. When a desired film thickness is formed, the glow discharge is stopped, the source gas introduction valve 109 is closed, and the source gas is allowed to flow into the deposition chamber 101. Stop and once return to high vacuum in the deposition chamber, finish the layer formation. This procedure is repeated a desired number of times to produce an electrophotographic photosensitive member in which deposited films having various functions are laminated.
[0036]
An example of the method for forming a deposited film of the present invention using the deposited film forming apparatus of FIG. 2 is performed as follows.
First, an auxiliary substrate 207 is attached to a deposition target substrate (also serving as a first electrode) 202 whose surface has been mirror-finished using a lathe, for example, and the deposition target substrate 202 and the auxiliary substrate 207 are attached to the heater 203 in the deposition chamber 201. The base body 207 is inserted.
[0037]
Next, after the source gas introduction valve 209 is closed and the deposition chamber is once evacuated from the exhaust port 215, the source gas introduction valve 209 is opened and a heating inert gas, for example, argon is supplied from the source gas discharge pipe 205. And the flow rate of the inert gas for heating is adjusted while monitoring the pressure gauge 210 so that the deposition chamber has a desired pressure. Thereafter, the temperature controller (not shown) is operated to heat the substrate 202 by the heater 203, and when the substrate 202 is heated to a desired temperature, the source gas introduction valve 209 is closed and the inert gas flows into the deposition chamber. Stop.
[0038]
The deposition film is formed by opening the source gas introduction valve 109 and depositing a predetermined source gas, for example, a source gas such as silane gas, disilane gas, methane gas, and ethane gas, and a doping gas such as diborane gas and phosphine gas from the source gas introduction port 205. The pumping speed is adjusted so that the pressure is introduced into 101 and maintained at a desired pressure of several mTorr to several Torr. Adjustment methods include adjusting the opening of the main valve (not shown) as appropriate, adjusting using the conductance adjustment valve (not shown), and combining an exhaust system (not shown) with a mechanical booster pump and a rotary pump. There are methods to adjust the rotational frequency of the mechanical booster pump. After the pressure is stabilized, the high frequency power supply 212 is turned on to cause glow discharge.
[0039]
At this time, high-frequency power with an oscillation frequency of less than 20 MHz is input when a certain layer is formed, and high-frequency power with an oscillation frequency of 50 MHz or more and 450 MHz or less is input when another layer is formed. Which layer is formed is appropriately selected as to whether high frequency power of less than 20 MHz or high frequency power of 50 MHz or more and 450 MHz or less is input.
[0040]
In either case, the matching circuit 211 is adjusted so that the reflected wave is minimized. The value obtained by subtracting the reflected power from the high frequency incident power is adjusted to a desired value. When a desired film thickness is formed, the glow discharge is stopped, the source gas introduction valve 209 is closed, and the source gas flows into the deposition chamber 201. And the formation of the layer is completed after the inside of the deposition chamber is returned to a high vacuum. This procedure is repeated a desired number of times to produce an electrophotographic photosensitive member in which deposited films having various functions are laminated.
[0041]
1 and FIG. 2, in the case of providing a change layer in which the composition or the like is continuously changed between the layers, for example, in the case of providing an intermediate layer between the photoconductive layer and the surface layer, After the photoconductive layer is formed by the above operation, the flow rate condition of the source gas is gradually and continuously changed from the condition at the time of photoconductive layer formation to the condition at the time of surface layer formation without stopping the supply of high-frequency power. And the like. At this time, the high frequency power sources 112 and 212 must be capable of varying the oscillation frequency, and the matching units 111 and 211 must be capable of covering the corresponding frequency band. At the same time as changing the flow rate of the source gas, the output of the high-frequency power sources 112 and 212 and the main valve are changed so that the oscillation frequency of the high-frequency power sources 112 and 212 is changed, and at the same time, the desired conditions for forming the change layer are obtained 104 etc. are adjusted as needed. Needless to say, when the flow rate of the raw material gas is changed, sufficient consideration should be given so that an extreme pressure change due to a gas protrusion or the like does not occur. As described above, the thickness of the layer in the change region may be a thickness that substantially forms an interface between the photoconductive layer and the surface layer.
[0042]
It goes without saying that all the outflow valves other than the necessary gases are closed when forming the respective layers, and in order to prevent the respective gases from remaining in the deposition chamber and the piping of the gas supply system. Temporarily evacuate to high vacuum as necessary. Needless to say, the above-described gas types and valve operations can be changed according to the production conditions of each layer.
[0043]
The material of the second electrode is copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, or a composite material of two or more of these materials. Preferably used. The shape is preferably cylindrical, but may be oval or polygonal as required. The second electrode may be provided with cooling means as necessary. As specific cooling means, cooling by water, air, liquid nitrogen, a Beltier element or the like is applied.
[0044]
The first electrode has a role as a film formation substrate and may be any material having a material, shape, or the like corresponding to the purpose of use. Regarding the shape, a cylindrical shape is desirable when it is used in an electrophotographic photosensitive member, but it may be a flat plate shape or other shapes as necessary. In terms of materials, copper, aluminum, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, stainless steel, and composite materials of two or more of these materials, polyester, polyethylene, An insulating material such as polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, glass, ceramics, paper, or the like coated with a conductive material can be used.
[0045]
The substrate temperature near the center of the cylindrical substrate is generally 100 ° C. or higher and 400 ° C. or lower, preferably 150 ° C. or higher and 350 ° C. or lower, more preferably 200 ° C. or higher and 350 ° C. or lower, which reduces dangling bonds in the film. It is desirable for a dense film.
[0046]
The heating element constituting the substrate heating heater may be vacuum type. More specifically, the heating element is an electric resistance heating element such as a sheath heater, plate heater, ceramic heater, carbon heater, liquid, gas, or the like. Examples include a heating element by heat exchange means. A heat-radiating lamp heating element such as a halogen lamp or an infrared lamp can also be suitably used as the substrate heater of the present invention. In this case, a lamp with higher power is installed at the end of the heater than the lamp installed in the center. Therefore, it is necessary to form a temperature gradient. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat resistant polymer resin, and the like can be used.
[0047]
The substrate material used in the present invention may be conductive or electrically insulating. Examples of the conductive material include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. In the case of electrically insulating materials such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, and other synthetic resin films, glass, ceramics, etc. Use with conductive treatment.
[0048]
The substrate used in the present invention may have a cylindrical or plate-like endless belt shape having a smooth surface or an uneven surface, and the thickness thereof is appropriately set so as to form a desired electrophotographic light-receiving member. However, if flexibility as an electrophotographic light receiving member is required, the thickness can be made as thin as possible within a range where the function as a substrate can be sufficiently exhibited. However, the substrate is usually preferably 10 μm or more from the standpoints of mechanical strength and the like in manufacturing and handling.
[0049]
In particular, when performing image recording using coherent light such as laser light, in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in visible images, unevenness is provided on the surface of the substrate. Also good. The unevenness provided on the surface of the substrate is created by a known method described in JP-A-60-168156, JP-A-60-178457, JP-A-60-225854, or the like.
[0050]
As another method for more effectively eliminating the image defect due to the interference fringe pattern when coherent light such as laser light is used, the surface of the substrate may be provided with an uneven shape by a plurality of spherical trace depressions. That is, the surface of the substrate has unevenness slightly smaller than the resolution required for the electrophotographic light receiving member, and the unevenness is due to a plurality of spherical trace depressions. Concavities and convexities due to a plurality of spherical trace depressions provided on the surface of the substrate are created by a known method described in Japanese Patent Application Laid-Open No. 61-231561.
[0051]
The charge injection blocking layer of the blocking type electrophotographic photosensitive member suitable for manufacturing with the manufacturing apparatus of the present invention is a photoconductive layer from the substrate side when the photoreceptive layer is subjected to charging treatment with a certain polarity on its free surface. It has a function of preventing the charge from being injected into the layer side, and has a so-called polarity dependency in which such a function is not exhibited when subjected to a reverse polarity charging process. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. The atoms controlling the conductivity contained in this layer may be distributed uniformly in the layer, or evenly distributed in the layer thickness direction, but distributed unevenly. There may be a part contained in the state. If the distribution concentration is non-uniform, it is preferable to contain it so that it is distributed more on the substrate side. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to uniformly contain the material in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction.
[0052]
Examples of the atoms that control the conductivity contained in the charge injection blocking layer include so-called impurities in the semiconductor field. The atoms belonging to Group IIIb of the periodic table that give p-type conductivity (hereinafter referred to as “IIIb”). Or an atom belonging to Group Vb of the periodic table that gives n-type conductivity (hereinafter abbreviated as “Group Vb atom”). Specific examples of Group IIIb atoms include B (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and B, Al, and Ga are particularly preferable. . Specific examples of the Group Vb atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and P and As are particularly preferable.
[0053]
The content of the atoms controlling the conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved, but is preferably 10 to 1 × 10.^Four Atomic ppm, more preferably 50-5 × 10^Three Atomic ppm, optimally 1 × 10² ~ 1x10^Three The atomic ppm is desirable.
[0054]
Further, the charge injection blocking layer contains at least one of carbon atom, nitrogen atom and oxygen atom, thereby improving the adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer. More can be achieved.
The carbon atoms, nitrogen atoms and / or oxygen atoms contained in the charge injection blocking layer may be uniformly distributed in the layer, or may be contained in the layer thickness direction. There may be a portion that is contained in a non-uniformly distributed state. However, in any case, it is necessary for the surface parallel to the surface of the substrate to be contained in a uniform distribution evenly from the point of achieving uniform characteristics in the in-plane direction.
[0055]
The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire layer region of the charge injection blocking layer is appropriately determined so that the object of the present invention can be effectively achieved. In the case of 2 or more types, the total amount is preferably 1 × 10^-3~ 50 atomic%, more preferably 5 x 10^-3~ 30 atomic%, optimally 1 x 10^-2-10 atomic% is desirable.
[0056]
When a hydrogen atom and / or a halogen atom is contained in the charge injection blocking layer, dangling bonds existing in the layer are compensated, and the film quality is improved. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1 to 50 atom%, more preferably 5 to 40 atom%, and most preferably 10 to 30 atoms. % Is desirable.
[0057]
The thickness of the charge injection blocking layer is preferably 0.1 to 5 [mu] m, and most preferably 1 to 4 [mu] m from the viewpoint of obtaining desired electrophotographic characteristics and economic effects.
[0058]
In order to form a charge injection blocking layer having characteristics capable of achieving the object of the present invention, the mixing ratio of the Si supply gas and the dilution gas, the gas pressure in the reaction vessel, the discharge power, and the temperature of the substrate are appropriately set. It is necessary to.
[0059]
Dilution gas H₂ The optimum flow rate of He and / or He is appropriately selected according to the layer design.₂ Is usually controlled in the range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.
[0060]
Similarly, the optimum gas pressure in the reaction vessel is appropriately selected according to the layer design.^-Four-10 Torr, preferably 5x10^-Four~ 5 Torr, optimally 1x10^-3˜1 Torr is preferred.
[0061]
Similarly, the optimum range of the discharge power is also selected according to the layer design. However, the discharge power relative to the flow rate of the gas for supplying Si is normally 0.5 to 7 times, preferably 1 to 6 times optimal Is preferably set in a range of 1.5 to 5 times.
[0062]
Similarly, the optimum range of the temperature of the substrate is also appropriately selected according to the layer design, but it is usually set to a range of 100 ° C. to 400 ° C., preferably 150 ° C. to 350 ° C., and most preferably 200 ° C. to 350 ° C. .
[0063]
The photoconductive layer of the electrophotographic photosensitive member suitable for production by the production apparatus of the present invention needs to contain hydrogen atoms and / or halogen atoms, which is a dangling bond of silicon atoms. This is indispensable in order to compensate for the above and improve the layer quality, in particular, the photoconductivity and the charge retention characteristics.
[0064]
The content of hydrogen atom or halogen atom, or the total amount of hydrogen atom and halogen atom is 10 to 30 atom%, more preferably 15 to 25 atom%, based on the sum of silicon atom and hydrogen atom or / and halogen atom. desirable.
[0065]
As a substance that can be a gas for supplying Si used in the present invention, SiH_Four , Si₂ H₆ , Si_Three H₈ , Si_Four H_TenIt is mentioned that silicon hydrides (silanes) that are in a gas state or can be gasified are effectively used. Further, in terms of easy handling during layer formation, good Si supply efficiency, etc., SiH_Four , Si₂ H₆ Is preferable. Then, hydrogen atoms are structurally introduced into the formed photoconductive layer so as to make it easier to control the introduction ratio of hydrogen atoms, and in order to obtain film characteristics that achieve the object of the present invention, It is necessary to form a layer by mixing a desired amount of hydrogen or a silicon compound gas containing hydrogen atoms with the above gas. In addition, each gas may be mixed in a plurality of types at a predetermined mixing ratio as well as a single type.
[0066]
Further, as the raw material gas for supplying halogen atoms used in the present invention, for example, halogen gases, halides, halogen-containing interhalogen compounds, halogen-substituted silane derivatives, etc. are gaseous or gasifiable halogen compounds. Are preferred. Further, a silicon hydride compound containing a halogen atom, which is gaseous or can be gasified, containing silicon atoms and halogen atoms as constituent elements can also be mentioned as effective. Specific examples of halogen compounds that can be suitably used in the present invention include fluorine gas (F₂ ), BrF, ClF, ClF_Three , BrF_Three , BrF_Five , IF_Three , IF₇ And interhalogen compounds. Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include Si₂ F_Four , Si₂ F₆ And the like. Preferred examples thereof include silicon fluoride.
[0067]
In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer, for example, the temperature of the substrate, introduction of the source material used to contain hydrogen atoms and / or halogen atoms into the deposition chamber What is necessary is just to control the quantity to perform, discharge electric power, etc.
[0068]
In the present invention, the photoconductive layer preferably contains an atom for controlling conductivity as required. Atoms that control conductivity may be contained in the photoconductive layer in a uniformly distributed state, or even if there are parts that are contained in a non-uniformly distributed state in the layer thickness direction. Good.
[0069]
Examples of the atoms that control conductivity include so-called impurities in the semiconductor field, and group IIIb atoms that give p-type conduction characteristics or group Vb atoms that give n-type conduction characteristics can be used.
[0070]
Specific examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. is there. Specific examples of the group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). P and As are particularly preferable.
[0071]
The content of atoms controlling the conductivity contained in the photoconductive layer is preferably 1 × 10^-2~ 1x10^Four Atomic ppm, more preferably 5 × 10^-2~ 5x10^Three Atomic ppm, optimally 1 × 10^-1~ 1x10^Three The atomic ppm is desirable.
[0072]
In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a raw material for introducing a group IIIb atom or a group Vb atom is introduced during the layer formation. The raw material for use may be introduced into the reaction vessel in a gas state together with another gas for forming the photoconductive layer. As a source material for introducing a group IIIb atom or a source material for introducing a group Vb atom, a material that is gaseous at normal temperature and pressure or that can be easily gasified at least under layer formation conditions is adopted. Is desirable.
[0073]
Specifically, as a raw material for introducing a group IIIb atom, B₂ H₆ , B_Four H_Ten, B_Five H₉ , B_Five H₁₁, B₆ H_Ten, B₆ H₁₂, B_TenH₁₄Boron hydride such as BF_Three , BCl_Three , BBr_Three Boron halide such as AlCl_Three , GaCl_Three , Ga (CH_Three )_Three , InCl_Three , TlCl_Three Etc.
[0074]
As a raw material for introducing a group Vb atom, it is effective to use PH for introducing a phosphorus atom._Three , P₂ H_Four Phosphorus hydrides such as PH_Four I, PF_Three , PF_Five , PCl_Three , PCl_Five , PBr_Three , PBr_Five , PI_Three And the like. In addition, AsH_Three , AsF_Three , AsCl_Three , AsBr_Three , AsF_Five , SbH_Three , SbF_Three , SbF_Five , SbCl_Three , SbCl_Five , BiH_Three , BiCl_Three , BiBr_Three Can also be mentioned as effective starting materials for the introduction of Group Vb atoms. In addition, if necessary, the starting material for introducing atoms for controlling the conductivity is H₂ And / or diluted with He.
[0075]
In the present invention, the thickness of the photoconductive layer is appropriately determined from the viewpoints of desired electrophotographic characteristics and economic effects, and is preferably 20 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm.
[0076]
In order to achieve the object of the present invention and form a photoconductive layer having desired film characteristics, the mixing ratio of Si supply gas and dilution gas, gas pressure in the deposition chamber, discharge power, and substrate temperature are appropriately set. It is necessary to. H used as dilution gas₂ The flow rate of He and / or He is appropriately selected in accordance with the layer design, but the dilution gas is usually 3 to 20 times, preferably 4 to 15 times, and most preferably 5 to the Si supply gas. It is desirable to control within a range of 10 times.
[0077]
Similarly, the optimum gas pressure in the deposition chamber is appropriately selected according to the layer design.^-Four-10 Torr, preferably 5x10^-Four~ 5 Torr, optimally 1x10^-3˜1 Torr is preferred.
[0078]
Similarly, the optimum range of the discharge power is also selected according to the layer design. However, the discharge power relative to the flow rate of the gas for supplying Si is normally 0.5 to 7 times, preferably 1 to 6 times optimal Is preferably set in a range of 1.5 to 5 times.
[0079]
Similarly, the optimum range of the temperature of the substrate is also appropriately selected according to the layer design, but it is usually set to a range of 100 ° C. to 400 ° C., preferably 150 ° C. to 350 ° C., and most preferably 200 ° C. to 350 ° C. .
[0080]
In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the substrate temperature and gas pressure for forming the photoconductive layer, but the conditions are not usually determined separately, but the desired characteristics are It is desirable to determine an optimum value based on mutual and organic relevance in order to form the light receiving member.
[0081]
The electrophotographic photosensitive member suitable for production with the production apparatus of the present invention preferably further comprises an amorphous silicon-based surface layer on the photoconductive layer. This surface layer has a free surface, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability. In the present invention, each of the amorphous materials forming the photoconductive layer and the surface layer constituting the photoreceptive layer has a common component called a silicon atom, so that chemical stability is obtained at the stacking interface. Is sufficiently secured.
[0082]
The surface layer may be made of any material as long as it is an amorphous silicon-based material. For example, the surface layer contains hydrogen atoms (H) and / or halogen atoms (X), and further contains amorphous silicon (hereinafter referred to as carbon atoms). Amorphous silicon (hereinafter referred to as “a-SiO: H, X”) containing hydrogen atoms (H) and / or halogen atoms (X) and further containing oxygen atoms (hereinafter referred to as “a-SiC: H, X”) Amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) and further containing nitrogen atoms (hereinafter referred to as “a-SiN: H, X”), hydrogen atoms (H) and / or Or amorphous silicon containing halogen atom (X) and further containing at least one of carbon atom, oxygen atom and nitrogen atom (hereinafter referred to as “a-SiCON: H, X”), etc. Material is suitably used.
[0083]
The surface layer material used in the present invention may be any amorphous material containing silicon, but is preferably a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen, particularly a-SiC. The main component is preferred.
The amount of carbon when the surface layer is composed mainly of a-SiC is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.
[0084]
In the present invention, it is necessary for the surface layer to contain hydrogen atoms and / or halogen atoms. This compensates for dangling bonds of silicon atoms, and improves layer quality, particularly photoconductive properties and charge retention. Indispensable to improve the characteristics. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms. The fluorine atom content is usually 0.01 to 15 atom%, preferably 0.1 to 10 atom%, and most preferably 0.6 to 4 atom%.
[0085]
As a substance that can be a silicon (Si) supply gas used in the formation of the surface layer of the present invention, SiH_Four , Si₂ H₆ , Si_Three H₈ , Si_Four H_TenIn particular, silicon hydrides (silanes) that can be gasified or can be gasified include SiH in terms of easy handling during layer formation and good Si supply efficiency._Four , Si₂ H₆ Is preferred. In addition, these source gases for supplying Si are supplied with H as required.₂ , He, Ar, Ne or the like may be used after being diluted.
[0086]
Examples of substances that can serve as carbon supply gas include CH_Four , C₂ H₆ , C_Three H₈ , C_Four H_TenHydrocarbons that can be gasified or can be gasified, etc., and CH in terms of ease of handling during layer formation, good Si supply efficiency, etc._Four , C₂ H₆ Is preferred. In addition, these carbon supply source gases can be replaced with H as required.₂ , He, Ar, Ne or the like may be used after being diluted.
[0087]
Examples of substances that can serve as nitrogen or oxygen supply gas include NH_Three , NO, N₂ O, NO₂ , O₂ , CO, CO₂ , N₂ And the like in the gas state. In addition, the source gas for supplying nitrogen and oxygen can be replaced with H if necessary.₂ , H_e , A_r , N_e It may be diluted with a gas such as
[0088]
Further, in order to further easily control the introduction ratio of hydrogen atoms introduced into the surface layer to be formed, hydrogen gas or a gas of a silicon compound containing hydrogen atoms is further mixed with these gases in a desired amount. It is preferable to form. In addition, each gas may be mixed not only with a single species but also with a plurality of species at a predetermined mixing ratio.
[0089]
Examples of effective source gases for supplying halogen atoms include gaseous or gasatable halogen compounds such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen. Furthermore, a silicon hydride compound containing a gaseous atom or a gasizable halogen atom containing silicon atoms and halogen atoms as constituent elements can also be mentioned as effective. Specific examples of halogen compounds that can be suitably used in the present invention include fluorine gas (F₂ ), BrF, ClF, ClF_Three , BrF_Three , BrF_Five , IF_Three , IF₇ And interhalogen compounds. Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include SiF_Four , Si₂ F₆ Etc. are preferred.
[0090]
In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer, for example, the temperature of the substrate, introduction of the raw material used for containing hydrogen atoms and / or halogen atoms into the deposition chamber What is necessary is just to control the quantity to perform, discharge electric power, etc.
[0091]
Carbon atoms and / or oxygen atoms and / or nitrogen atoms may be contained uniformly in the surface layer, or may have a non-uniform distribution in which the content varies in the layer thickness direction of the surface layer. There may be parts.
[0092]
The thickness of the surface layer in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. When the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the photoreceptor, and when the layer thickness exceeds 3 μm, electrophotographic characteristics such as an increase in residual potential are observed. .
[0093]
Similarly, an optimum range of the gas pressure in the deposition chamber is selected as appropriate according to the layer design.^-FourTo 10 Torr, more preferably 5 × 10^-Four~ 5 Torr, optimally 1x10^-3~ 1 Torr.
[0094]
Similarly, the optimum range of the temperature of the substrate is also appropriately selected according to the layer design, but it is usually set to a range of 100 ° C. to 400 ° C., preferably 150 ° C. to 350 ° C., and most preferably 200 ° C. to 350 ° C. .
[0095]
The electrophotographic photosensitive member produced by the apparatus of the present invention is not only used in electrophotographic copying machines but also widely used in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate-making machines. Can be used.
[0096]
【Example】
  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
  referenceExample 1
  In the deposited film forming apparatus shown in FIG. 1, an a-Si film was formed on a cylindrical substrate made of aluminum to produce an electrophotographic photoreceptor. Manufacturing conditions other than the discharge are shown in Table 1. After film formation of the lower blocking layer using a high frequency power source with an oscillation frequency of 105 MHz, the discharge is temporarily cut off, the high frequency power source is replaced with a 13.56 MHz one, and the photoconductive layer and the surface protective layer are formed by the same procedure as before. A film was formed.
[0097]
[Table 1]

The obtained electrophotographic photoreceptor was evaluated by the following method.
[0098]
Each photoconductor was set in an electrophotographic apparatus (an Canon NP6060 modified for experiment), and the electrophotographic characteristics such as initial charging ability and residual potential were evaluated as follows.
[0099]
Charging ability: An electrophotographic photoreceptor is installed in an experimental apparatus, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential of the dark part of the electrophotographic photoreceptor is measured with a surface potential meter.
[0100]
Uneven charging: The electrophotographic photosensitive member is set in an electrophotographic apparatus, a high voltage of +6 kV is applied to the charger to perform corona charging, and the surface potential of the dark part of the electrophotographic photosensitive member is measured at the development position with a surface potential meter. Five points are measured in the axial direction of the electrophotographic photosensitive member, and potential unevenness at this time is evaluated.
[0101]
Sensitivity unevenness: The electrophotographic photosensitive member is charged to a constant dark portion surface potential. Immediately using a filter, a halogen lamp light excluding light having a wavelength region of 600 nm or more is irradiated, and the light quantity is adjusted so that the bright portion surface potential of the electrophotographic photosensitive member becomes a predetermined value. The amount of light required at this time is converted from the lighting voltage of the halogen lamp light source. In this procedure, the five-point sensitivity is measured in the axial direction of the electrophotographic photosensitive member, and the sensitivity unevenness at this time is evaluated.
[0102]
Residual potential: The electrophotographic photosensitive member is charged to a constant dark portion surface potential. Immediately after that, a relatively strong light with a certain amount of light is irradiated. The light image was irradiated with light using a halogen lamp light source, except for light having a wavelength region of 600 nm or more, using a filter. At this time, the surface potential of the bright part of the electrophotographic photosensitive member is measured with a surface potential meter.
[0103]
Density unevenness: The surface potential of the electrophotographic photosensitive member is charged to a predetermined dark portion surface potential at the development position. Immediately after that, a halogen lamp is used as a light source, and a filter is used to irradiate light excluding light having a wavelength region of 600 nm or more, and the amount of light when the surface potential is 50 V is measured. Next, after charging to a predetermined surface potential in the same manner as described above, the light is irradiated with a light amount ½ of the light amount, and development is performed by a developing device. The image density at this time was evaluated by measuring five points in the axial direction of the electrophotographic photosensitive member. However, the image density was measured using an image densitometer: Macbeth RD914.
[0104]
Image flow: A test chart in which black and white portions shown in FIG. 4 are arranged with a constant width a is prepared as a document at the time of image formation under a high temperature and high humidity environment (temperature: 30 ° C., humidity: 80%). When the line width a was narrowed, the evaluation was performed using the minimum line width a that can be reproduced and resolved on the copy image. In other words, when the line width a in the test chart is reduced, if the line width a becomes equal to or smaller than a certain line width a, minute blur due to the image flow of the outline of the adjacent black portion on the image overlaps, effectively making the resolution impossible. End up. The numerical value of the line width a at that time was evaluated as representing the degree of image flow.
[0105]
White spot: Evaluation was made based on the number of white spots with a diameter of 0.2 mm or more within the same area of a copy image obtained by copying a full black chart (part number: FY9-9073) made by Canon on a document table. The classification of evaluation is as follows.
For each
◎ Very good
○ Good
△ No problem in practical use at conventional level
× Practical problems
Film adhesion test: 100 g of iron balls were dropped from a height of 50 cm and collided with the electrophotographic photosensitive member. The dents produced at this time were observed in detail, and the adhesion between the a-Si film and the substrate was evaluated.
[0106]
◎ No cracks or film peeling on the film around the dent, very good
〇 Slight cracking but no film peeling, good
△ There are cracks, but there is no film peeling and there is no practical problem.
× Peeling occurs on the film around the dent, causing problems in practice
Film formation time: The film formation time with respect to the total film formation time of Comparative Example 1 was evaluated.
[0107]
            ◎ Film formation time is 10% or more shorter than Comparative Example 1.
            〇 Film formation time is about 10% shorter than Comparative Example 1.
            △ Almost the same time as Comparative Example 1
            × Film formation time longer than Comparative Example 1
  The above evaluation results were evaluated in the same manner as described later.Reference Example 2,Example1~4The results are shown in Table 2 together with the results of Comparative Examples 1 and 2.
[0108]
  referenceExample 2
  Other than changing the operating oscillation frequencyreferenceIn the same manner as in Example 1, an electrophotographic photoreceptor was prepared. After the lower blocking layer to the photoconductive layer were formed using a high frequency power source with an oscillation frequency of 13.56 MHz, the discharge was temporarily stopped, and the high frequency power source was replaced with a 105 MHz one to form a surface protective layer.
  Example1
  Other than changing the operating oscillation frequencyreferenceIn the same manner as in Example 1, an electrophotographic photoreceptor was prepared. In the lower blocking layer, film formation was performed using a high frequency power source with an oscillation frequency of 13.56 MHz, and then the discharge was temporarily stopped, and the photoconductive layer was formed by replacing the high frequency power source with that of 105 MHz. Further, after the film formation of the photoconductive layer was completed, the discharge was once stopped, and the power supply was returned to 13.56 MHz again to form a surface protective layer.
  Example2
  Other than changing the operating oscillation frequencyreferenceIn the same manner as in Example 1, an electrophotographic photoreceptor was prepared. The lower blocking layer was formed using a high frequency power source with an oscillation frequency of 105 MHz, and then the discharge was temporarily stopped, and the high frequency power source was replaced with a 13.56 MHz one to form a photoconductive layer. Further, after the film formation of the photoconductive layer was completed, the discharge was temporarily stopped, and the power source was returned to 105 MHz again to form a surface protective layer.
  Example3
  In the deposited film forming apparatus shown in FIG. 2, an a-Si film was formed in accordance with the manufacturing conditions (excluding internal pressure) shown in Table 1 for a cylindrical substrate made of aluminum to produce an electrophotographic photoreceptor. In this embodiment, the oscillation frequency of the high frequency power source that uses the lower blocking layer to the photoconductive layer at the oscillation frequency is 80 MHz, the internal pressure is 0.05 Torr, and the other layers are formed using the high frequency power source of 10 MHz and the internal pressure is 0.5 Torr. The film was formed.
  Example4
  Example with the exception of changing the oscillation frequency used3In the same manner as described above, an electrophotographic photoreceptor was prepared. The oscillation frequency of the high-frequency power source used in the photoconductive layer to the surface layer was 60 MHz, the inner pressure was formed at 0.04 Torr, and the lower blocking layer was formed at the inner pressure of 0.45 Torr using a 15 MHz high-frequency power source.
  Comparative Example 1
  In the deposited film forming apparatus shown in FIG. 1, a high frequency power source having an oscillation frequency of 13.56 MHz was installed, an a-Si film was formed on a cylindrical substrate made of aluminum, and an electrophotographic photoreceptor was prepared. In this comparative example, the lower blocking layer, the photoconductive layer, and the surface protective layer were all formed by a high frequency power source having an oscillation frequency of 13.56 MHz according to the manufacturing conditions shown in Table 1.
  Comparative Example 2
  In the deposited film forming apparatus shown in FIG. 2, a high frequency power source having an oscillation frequency of 13.56 MHz was installed, an a-Si film was formed on a cylindrical substrate made of aluminum, and an electrophotographic photoreceptor was prepared. In this comparative example, the lower blocking layer, the photoconductive layer, and the surface protective layer were all formed by a high frequency power source having an oscillation frequency of 13.56 MHz according to the manufacturing conditions shown in Table 1.
[0109]
[Table 2]

[0110]
  As a result of the above, it was found that the electrophotographic photoreceptor of the present invention showed very good characteristics in all evaluations compared with the conventional photoreceptors shown in Comparative Examples 1 and 2, and the superiority of the present invention was clear. It became.
[0111]
  Reference example 3
  referenceAn a-Si film was formed on a cylindrical cylindrical substrate made of aluminum according to the production conditions shown in Table 1 by the same deposition film forming apparatus and procedure as in Example 1 to prepare an electrophotographic photoreceptor. However, in this embodiment, the high frequency oscillation frequency used in the lower blocking layer was changed from 105 MHz to 200 MHz. The internal pressure during film formation isreferenceSimilar to Example 1, 0.02 Torr. The electrophotographic photoreceptor thus prepared isReference Examples 1 and 2 and Examples 1 to 4Was evaluated using the same procedure asreferenceGood results similar to Example 1 were obtained.
Reference example 4
  referenceAn a-Si film was formed on a cylindrical substrate made of aluminum according to the manufacturing conditions shown in Table 1 by the same deposition film forming apparatus and procedure as in Example 2 to produce an electrophotographic photoreceptor. However, in this embodiment, the high frequency oscillation frequency used in the surface protective layer was changed from 105 MHz to 300 MHz. The internal pressure during film formation is 0.03 Torr as in Example 2. The electrophotographic photoreceptor thus prepared isReference Examples 1 and 2 and Examples 1 to 4Was evaluated using the same procedure asreferenceGood results similar to Example 2 were obtained.
  Example5
  Example1An a-Si film was formed on a cylindrical cylindrical substrate made of aluminum in accordance with the production conditions shown in Table 1 using the same deposition film forming apparatus and procedure as described above to prepare an electrophotographic photoreceptor. However, in this embodiment, the high frequency oscillation frequency used in the photoconductive layer was changed from 105 MHz to 50 MHz. Example of internal pressure during film formation1Like 0.03 Torr. The electrophotographic photoreceptor thus prepared isReference Examples 1 and 2 and Examples 1 to 4The evaluation was performed in the same procedure as in Example.1Good results similar to those obtained were obtained.
[0112]
【The invention's effect】
As described in detail above, in a method of manufacturing an electrophotographic photosensitive member made of an amorphous material having at least silicon atoms as a base material, a layer deposited by glow discharge excited by high-frequency power having an oscillation frequency of less than 20 MHz. And a layer deposited by glow discharge excited by high-frequency power with an oscillation frequency of 50 MHz or more and 450 MHz or less can be formed so that a substrate having a relatively large area can be plasma-treated at a high processing speed. High charging performance, high image density, short production time, low cost, no deterioration in image quality even when used in high temperature and high humidity environments, and even if there are some fluctuations in the manufacturing process It is possible to provide an electrophotographic photosensitive member that does not cause trouble such as peeling, is stable, has good reproducibility, and is easy to manage the manufacturing process.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of an apparatus used in a method for forming an electrophotographic photosensitive member of the present invention.
FIG. 2 is a schematic view showing another example of an apparatus used in the method for forming an electrophotographic photosensitive member of the present invention.
FIG. 3 is a schematic view showing an example of an apparatus used in a conventional method for forming an electrophotographic photosensitive member.
FIG. 4 is a schematic diagram of an image flow test chart of the electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
101, 201, 301 Deposition chamber
102, 202, 302 First electrode also serving as a film formation substrate
103, 203, 303 Heating heater
104, 304 Main valve
105, 205, 305 Source gas discharge pipe
106, 206, 306 Second electrode
107, 207, 307 Auxiliary substrate
108,308 Exhaust device
109, 209, 309 Source gas introduction valve
110, 210, 310 Pressure gauge
111, 211, 311 Matching device
112, 212, 312 High frequency power supply
113, 313 Insulation material
114, 314 Insulated furnace wall
115, 215, 315 Exhaust port

Claims (4)

A conductive cylindrical substrate is installed in a vacuum-tight deposition chamber connected to an exhaust means and equipped with a source gas supply means, and a gaseous source containing at least silicon atoms is decomposed by glow discharge excited by high-frequency power. In the manufacturing method of manufacturing an electrophotographic photosensitive member by depositing an amorphous material having at least silicon atoms as a base material on the cylindrical substrate,
The electrophotographic photoreceptor deposited layer on the cylindrical substrate a blocking type comprises at least a lower blocking layer and a photoconductive layer, or 50MHz said photoconductive layer, it is formed using the following high-frequency power 450 MHz, the method of forming the electrophotographic photosensitive member and forming a layer other than the photoconductive layer using a RF power of less than 20MHz. The electrophotographic have photoreceptor surface protective layer, a method of forming the electrophotographic photosensitive member according to claim 1, the surface protective layer and forming using a high frequency power of less than 20 MH z. A conductive cylindrical substrate is installed in a vacuum-tight deposition chamber connected to an exhaust means and equipped with a source gas supply means, and a gaseous source containing at least silicon atoms is decomposed by glow discharge excited by high-frequency power. In the manufacturing method of manufacturing an electrophotographic photosensitive member by depositing an amorphous material having at least silicon atoms as a base material on the cylindrical substrate,
The electrophotographic deposited layer on the cylindrical substrate photoconductor an elimination of at least a lower blocking layer, photoconductive layer, made of the surface protective layer, the lower blocking layer and the surface protective layer 50MHz or higher, 450 MHz or less the formed using high frequency power, a method of forming the electrophotographic photosensitive member, characterized in that said lower blocking layer and a layer other than the surface protective layer is formed using a high frequency power of less than 20MHz. A conductive cylindrical substrate is installed in a vacuum-tight deposition chamber connected to an exhaust means and equipped with a source gas supply means, and a gaseous source containing at least silicon atoms is decomposed by glow discharge excited by high-frequency power. In the manufacturing method of manufacturing an electrophotographic photosensitive member by depositing an amorphous material having at least silicon atoms as a base material on the cylindrical substrate,
The electrophotographic photoreceptor is a blocking type, and the deposition layer on the cylindrical substrate has a lower blocking layer, a photoconductive layer and a surface protective layer, and the lower blocking layer and the photoconductive layer are 50 MHz or more, A method for forming an electrophotographic photosensitive member, comprising: using a high frequency power of 450 MHz or less; and forming the surface protective layer using a high frequency power of less than 20 MHz.

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