JP2009179870A - Deposited film formation method and device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deposited film formation method and a device therefor with which a satisfactory deposited film having reduced film defects and characteristic unevenness can be deposited at high speed, and further, production of image defects such as the production of black spots in image formation using an electrophotographic photoreceptor is suppressed, so that image characteristics can be improved. <P>SOLUTION: Disclosed is a deposited film formation method including: a first step where, in a state that deposited film forming objects 10 are supported to a first conductor 20A and a second conductor 20B arranged so as to be separated from each other respectively, the deposited film forming objects 10 are stored in a reaction chamber 3; a second step where the reaction chamber 3 is made into a reaction gas atmosphere; and a third step where pulse-like d.c. voltage is applied to a space between the first conductor 20A and the second conductor 20B in such a manner that a state where the potential of the first conductor 20A is made higher than that of the second conductor 20A and a state where the potential of the second conductor 20B is made higher than that of the first conductor 20A are alternately repeated. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a technique for forming a deposited film, and more particularly to a deposited film forming technique suitable for forming an amorphous semiconductor film in an electrophotographic photosensitive member.

  Conventionally, an electrophotographic photoreceptor is manufactured by forming a photoconductive layer, a surface layer, or the like as a deposited film on the surface of a cylindrical substrate. As a method for forming a deposited film, a method (plasma CVD method) in which a decomposition product obtained by decomposing a source gas by high-frequency glow discharge is applied to a substrate is widely employed.

  In such a method for forming a deposited film, when the deposition rate of the photoconductive layer or surface layer in the electrophotographic photosensitive member is increased, the characteristics as the electrophotographic photosensitive member may be impaired. In recent years, electrophotographic photosensitive devices have been pursued with higher added value such as higher image quality, higher speed, and higher durability than ever before, and the film forming speed has been increased in order to satisfy these characteristics. It is forced to improve the film quality by lowering. On the other hand, when the deposition rate is reduced, there arises a problem that the manufacturing efficiency is deteriorated and the manufacturing cost is increased. Therefore, the deposition rate of the photoconductive layer and the surface layer is normally set to about 5 μm / h when these layers are formed as a-Si layers.

  On the other hand, in the plasma CVD method, various technical developments have been carried out in order to achieve a high film formation rate and appropriately maintain the characteristics as an electrophotographic photosensitive member. As an example, there is a microwave plasma CVD method using a microwave (see, for example, Patent Documents 1 and 2).

  In the method described in Patent Document 1, a source film is decomposed by supplying a microwave having a frequency of 2.45 GHz to a deposition chamber to form a deposited film. On the other hand, the method described in Patent Document 2 is a method of generating an electric field between a part of means for supplying a source gas and a substrate while supplying a microwave to the discharge space of the reaction vessel. When microwaves are used, since the degree of ionization of plasma is high and the plasma density is high, it is possible to form a deposited film having a high deposition rate and low internal stress. In particular, when an electric field is generated in addition to supplying microwaves, the ions in the plasma are accelerated by the electric field to increase the kinetic energy, thereby reducing the stress in the film and causing internal stress. Can be formed.

  There is also a method in which high-frequency power having a discharge frequency of 20 MHz or more is supplied to cause discharge between the first and second electrodes, and a DC or AC bias voltage is applied to the first electrode that also serves as the substrate to be processed. (For example, refer to Patent Document 3). In this method, the surface potential of the first electrode is made uniform and stable by applying a bias voltage, and the uneven distribution of plasma due to instability and non-uniformity of discharge in the low power region of the high-frequency power is suppressed. It is intended to improve the uniformity of the film quality.

JP-A-60-186849 JP-A-3-219081 JP-A-8-225947 International Publication WO / 2006/126690 Pamphlet

  However, in the microwave plasma CVD method, there is a problem that the film formation speed differs between the plasma irradiation region and the non-irradiation region, and a uniform film is difficult to obtain because the plasma is unevenly distributed. In particular, it is difficult to obtain a uniform film on a substrate that has a relatively large deposition area such as a cylindrical substrate and is difficult to simultaneously irradiate plasma on the entire surface. Further, when the frequency of the voltage applied between the pair of electrodes is made higher than 13.56 MHz, instability and non-uniformity of discharge occur, scratches occur on the surface of the substrate and the deposited film, or dust or the like When foreign matter adheres, the electric field concentrates on scratches and foreign matter, resulting in a film with many defects.

  Furthermore, when a bias voltage (electric field) is applied to the discharge region between a pair of electrodes, it is considered very effective for improving the film quality of the deposited film in high-speed film formation, but the film quality of the deposited film is deteriorated. Sometimes.

  More specifically, when the bias voltage applied to the discharge space increases, arc discharge is likely to occur in the discharge space. When arc discharge occurs, the total power applied to the bias electrode or the substrate is instantaneously concentrated in one place, and the substrate and the deposited film on the substrate may be destroyed. When such abnormal discharge occurs frequently, collision of active species with the substrate is not performed effectively, and the reproducibility of the characteristics of the deposited film is lowered.

  These problems can be suppressed or prevented by lowering the bias voltage applied between the pair of electrodes. However, when the bias voltage is lowered, the deposition rate of the deposited film is lowered. For this reason, it is extremely difficult to improve the film forming speed and the film quality characteristics. Further, the deterioration of film quality causes image defects such as black spots when the electrophotographic photosensitive member is incorporated in an image forming apparatus and used.

  The present invention makes it possible to form a good deposited film with little film defects and characteristic unevenness at high speed, and suppress image defects such as black spots in image formation using an electrophotographic photosensitive member, thereby improving image characteristics. The challenge is to improve.

  In the first aspect of the present invention, the deposition film formation target is accommodated in the reaction chamber in a state where the deposition film formation target is supported by each of the first conductor and the second conductor that are spaced apart from each other. A state in which the first conductor is at a higher potential than the second conductor between the first step and the second step in which the reaction chamber is in a reaction gas atmosphere, and the first conductor and the second conductor. And a third step of applying a pulsed DC voltage so as to alternately repeat a state in which the second conductor is at a higher potential than the first conductor. Is provided.

  Preferably, in the third step, when the pulsed DC voltage is supplied to the first conductor, the second conductor is set to a ground potential or a reference potential, while the second conductor is The first conductor is set to a ground potential or a reference potential when supplying a pulsed DC voltage.

  Preferably, further, in the third step, a negative pulsed DC voltage is applied between the first conductor and the second conductor.

  In the first step, for example, the deposited film forming object is formed in a state where one or a plurality of cylindrical conductive substrates as the deposited film forming object are supported on the first conductor and the second conductor, respectively. Is carried out in the reaction chamber.

  In the first step, a plurality of conductive substrates may be arranged in the axial direction of the conductive substrate on each of the first conductor and the second conductor.

  The cylindrical conductive substrate is, for example, a substrate for an electrophotographic photosensitive member.

  The first step is performed, for example, by supporting the deposited film forming object on each of a plurality of first conductors and a plurality of second conductors arranged concentrically.

  The plurality of first conductors and the plurality of second conductors are alternately arranged in the circumferential direction on the same circumference, for example. The plurality of first conductors may be disposed so as to surround the plurality of second conductors. In this case, it is preferable that the plurality of first conductors and the plurality of second conductors are arranged in a staggered manner in the circumferential direction.

  In the second aspect of the present invention, a reaction chamber for accommodating a plurality of deposition film formation objects and a plurality of deposition film formation objects that are spaced apart from each other in the reaction chamber and support the plurality of deposition film formation objects. The one or more first conductors and one or more second conductors, gas supply means for supplying a reactive gas into the reaction chamber, and between the first conductor and the second conductor, Applying a pulsed DC voltage so that the first conductor has a higher potential than the second conductor and the second conductor has a higher potential than the first conductor alternately. And a voltage applying means. A deposited film forming apparatus is provided.

  Preferably, the voltage applying means sets the second conductor to a ground potential or a reference potential when supplying a pulsed direct-current voltage to the first conductor, while applying a pulse shape to the second conductor. When the direct current voltage is supplied, the first conductor is configured to have a ground potential or a reference potential.

  Preferably, the voltage applying means is configured to apply a negative pulsed DC voltage between the first conductor and the second conductor.

  Each of the first conductor and the second conductor is configured to be able to support, for example, one or a plurality of cylindrical conductive substrates as the deposited film formation target.

  Each of the first conductor and the second conductor is configured to support the plurality of cylindrical conductive bases side by side in the axial direction of the conductive base.

  The cylindrical conductive substrate is, for example, a substrate for an electrophotographic photosensitive member.

  In the reaction chamber, for example, a plurality of first conductors and a plurality of second conductors are arranged concentrically.

  Preferably, the plurality of first conductors and the plurality of second conductors are alternately arranged in the circumferential direction on the same circumference. The plurality of first conductors may be disposed so as to surround the plurality of second conductors. In this case, the plurality of first conductors and the plurality of second conductors are arranged in a staggered manner in the circumferential direction.

  According to the present invention, it is possible to suppress arc discharge without reducing the film formation rate, and to form a good deposited film with less characteristic unevenness at a high speed without increasing defects. Therefore, it is possible to provide a high-quality deposited film with little film thickness unevenness and to provide an electrophotographic photosensitive member having such a high-quality deposited film.

  In the following, the present invention will be described as first to third embodiments with reference to the drawings, taking as an example the case of forming an electrophotographic photosensitive member.

  First, a first embodiment of the present invention will be described with reference to FIGS.

  An electrophotographic photoreceptor 1 shown in FIG. 1 is an example in which a deposited film is formed by the deposited film forming apparatus and method according to the present invention. A charge injection blocking layer 11 and a photoconductive layer are formed on the outer peripheral surface of a cylindrical substrate 10. The layer 12 and the surface layer 13 are sequentially laminated.

The cylindrical substrate 10 serves as a support base for the photoreceptor, and is formed to have conductivity at least on the surface. This cylindrical substrate 10 is made of, for example, aluminum (Al), stainless steel (SUS), zinc (Zn), copper (Cu), iron (Fe), titanium (Ti), nickel (Ni), chromium (Cr), tantalum ( The whole is formed of a metal material such as Ta), tin (Sn), gold (Au), silver (Ag), or an alloy material including the exemplified metal material as having conductivity. The cylindrical substrate 10 may also be formed by depositing a conductive film made of the exemplified metal material or a transparent conductive material such as ITO and SnO _{2 on} the surface of an insulator such as resin, glass, and ceramic. . As the material for forming the cylindrical substrate 10, it is most preferable to use an Al-based material among the exemplified materials, and it is particularly preferable to form the entire cylindrical substrate 10 from the Al-based material. Then, the electrophotographic photosensitive member 1 can be manufactured at a low weight and at a low cost, and when the charge injection blocking layer 11 and the photoconductive layer 12 are formed of an a-Si material, the layer and the cylinder are formed. The adhesion between the substrate 10 and the substrate 10 can be improved and the reliability can be improved.

  The charge injection blocking layer 11 is for blocking the injection of carriers (electrons) from the cylindrical substrate 10 and is made of, for example, an a-Si material. The charge injection blocking layer 11 is formed, for example, by adding a boron (B), nitrogen (N), or oxygen (O) as a dopant to a-Si. The thickness of the charge injection blocking layer 11 is, for example, 2 μm or more and 10 μm or less.

The photoconductive layer 12 is for generating carriers by light irradiation such as laser light, and is formed of, for example, an a-Si material or an a-Se material such as Se-Te or As ₂ Se _3. Yes. However, electrophotographic characteristics (for example, photoconductive characteristics, high-speed response, repeat stability, heat resistance or durability) and consistency with the surface layer 13 when the surface layer 13 is formed of an a-Si material are used. In consideration, the photoconductive layer 12 is preferably formed of a-Si or an a-Si material obtained by adding carbon (C), nitrogen (N), oxygen (O) or the like to a-Si. . The thickness of the photoconductive layer 12 may be appropriately set depending on the photoconductive material to be used and desired electrophotographic characteristics. When the photoconductive layer 12 is formed using an a-Si material, for example, It is 5 μm or more and 100 μm or less, preferably 10 μm or more and 80 μm or less.

The surface layer 13 is for protecting the surface of the electrophotographic photosensitive member 1, and a-Si such as a-SiC or a-SiN so as to be able to withstand abrasion due to rubbing in the image forming apparatus. It is formed of a system material or aC. The surface layer 13 has a sufficiently wide optical band gap with respect to the irradiated light so that light such as laser light irradiated to the electrophotographic photosensitive member 1 is not absorbed, It has a resistance value (generally 10 ¹¹ Ω · cm or more) that can hold an electrostatic latent image in image formation.

  The charge injection blocking layer 11, the photoconductive layer 12, and the surface layer 13 in the electrophotographic photosensitive member 1 are formed by using, for example, the plasma CVD apparatus 2 shown in FIGS.

  The plasma CVD apparatus 2 contains the first and second supports 20A and 20B in the vacuum reaction chamber 3, and further includes a voltage application means 4, a rotation means 5, a source gas supply means 6 and an exhaust means 7. Yes.

  The first and second supports 20A and 20B are for supporting the cylindrical base 10 and function as a first conductor and a second conductor, respectively. The first and second supports 20A and 20B are formed in a hollow shape having flange portions 21A and 21B, and are entirely formed of a conductive material similar to the cylindrical base 10 as a conductor. The first and second supports 20A and 20B are formed to have a length that can support the two cylindrical base bodies 10, and are detachable from the conductive columns 22A and 22B. Therefore, in the first and second supports 20A and 20B, the two cylindrical substrates 10 can be taken in and out of the vacuum reaction chamber 3 without directly touching the surfaces of the two cylindrical substrates 10 supported. it can.

  The conductive struts 22A and 22B are entirely formed of a conductive material similar to that of the cylindrical substrate 10 and are fixed to the plate 32 described later via insulating materials 23A and 23B. The voltage applying means 4 is connected to the conductive columns 22A and 22B via the conductive plates 24A and 24B. The insulating materials 23A and 23B serve to insulate the DC voltage applied from the voltage applying means 4 through the conductive plates 24A and 24B from other conductors.

  Heaters 26A and 26B are accommodated inside the conductive columns 22A and 22B via ceramic pipes 25A and 25B. The ceramic pipes 25A and 25B are for ensuring insulation and thermal conductivity. The heaters 26 </ b> A and 26 </ b> B are for heating the cylindrical substrate 10. As the heaters 26A and 26B, for example, a nichrome wire or a cartridge heater can be used.

  Here, the temperature of the first and second supports 20A and 20B is monitored by, for example, thermocouples (not shown) attached to the first and second supports 20A and 20B or the conductive columns 22A and 22B. . Therefore, the temperature of the cylindrical substrate 10 is a certain range selected from a target temperature range, for example, 200 ° C. or more and 400 ° C. or less by turning the heaters 26A and 26B on and off based on the monitoring results of the thermocouple. Maintained.

  The vacuum reaction chamber 3 is a space for forming a deposited film on the cylindrical substrate 10, and is defined by a gas blowing portion 30 and a pair of plates 31 and 32.

  The gas blowing part 30 is formed in a cylindrical shape surrounding the first and second supports 20A and 20B. The gas blowing portion 30 is formed in a hollow shape with the same conductive material as that of the cylindrical substrate 10 and is joined to a pair of plates 31 and 32.

  The gas blowing part 30 is formed in such a size that the shortest distance between the cylindrical base 10 supported by the first and second supports 20A and 20B and the gas blowing part 30 is 10 mm or more and 200 mm or less. Yes. This is because when the shortest distance between the cylindrical substrate 10 and the gas blowing portion 30 is smaller than 10 mm, workability cannot be sufficiently ensured when the cylindrical substrate 10 is taken in and out of the vacuum reaction chamber 3. When the shortest distance between the cylindrical substrate 10 and the gas blowing portion 30 is larger than 200 mm, the apparatus 2 becomes large and the productivity per unit installation area is deteriorated.

  The gas blowing part 30 is provided with a gas introduction port 35 and a plurality of gas blowing holes 36.

  The gas inlet 35 is for introducing a raw material gas to be supplied to the vacuum reaction chamber 3, and is connected to the raw material gas supply means 6.

  The plurality of gas blowing holes 36 are for blowing the raw material gas introduced into the gas blowing section 30 toward the cylindrical substrate 10 and are arranged at equal intervals in the vertical direction and the circumferential direction in the figure. . The plurality of gas blowing holes 36 are formed in a circular shape having the same shape, and the hole diameter is, for example, not less than 0.5 mm and not more than 2.0 mm. Of course, the diameter, shape, and arrangement of the plurality of gas blowing holes 36 can be changed as appropriate.

  The plate 31 is for selecting a state in which the vacuum reaction chamber 3 is opened or closed, and the first and second supports 20A for the vacuum reaction chamber 3 by opening and closing the plate 31. , 20B can be taken in and out. The plate 31 is formed of the same conductive material as that of the cylindrical base body 10, but a deposition preventing plate 37 is attached to the lower surface side. This prevents a deposited film from being formed on the plate 31. The deposition preventing plate 37 is also formed of the same conductive material as that of the cylindrical substrate 10, but the deposition preventing plate 37 is detachable from the plate 31. Therefore, the adhesion preventing plate 37 can be cleaned by removing it from the plate 31 and can be used repeatedly.

The plate 32 is a base of the vacuum reaction chamber 3 and is formed of the same conductive material as that of the cylindrical substrate 10. An insulating member 34 is provided on the upper surface side of the plate 32. The insulating member 34 has a role of suppressing the occurrence of arc discharge between the first and second supports 20A, 20B and the plate 32. The material for the insulating member 34 is not particularly limited as long as it is insulating, has sufficient heat resistance at the operating temperature, and emits a small amount of gas in a vacuum. Examples of the material for the insulating member 34 include glass materials (borosilicate glass, soda glass, heat-resistant glass, etc.), inorganic insulating materials (ceramics, quartz, sapphire, etc.), or synthetic resin insulating materials (Teflon (registered trademark)). Fluororesin, polycarbonate, polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyamide, vinylon, epoxy, mylar, PEEK material, etc.). However, the insulating member 34 has a thickness of a certain level or more in order to prevent the insulating member 34 from being used due to warpage due to the stress caused by the internal stress of the film formation body and the bimetal effect caused by the temperature increase during film formation. It is formed as having. For example, when the insulating member 34 is formed of a material having a coefficient of thermal expansion of 3 × 10 ⁻⁵ / K or more and 10 × 10 ⁵ / K or less, such as Teflon (registered trademark), the thickness of the insulating member 34 is 10 mm or more. Is set. When the thickness of the insulating member 34 is set within such a range, warpage caused by stress generated at the interface between the insulating member 34 and the a-Si film of 10 μm or more and 30 μm or less formed on the cylindrical substrate 10. The amount is set to 1 mm or less as a difference in height in the axial direction between the end portion and the central portion in the horizontal direction with respect to a length of 200 mm in the horizontal direction (radial direction substantially orthogonal to the axial direction of the cylindrical substrate 10). Therefore, the insulating member 34 can be used repeatedly.

  The plate 32 and the insulating member 34 are provided with gas discharge ports 32A and 34A. The gas exhaust ports 32A and 34A are for exhausting the gas inside the vacuum reaction chamber 3, and are connected to exhaust means (not shown). This exhaust means is for exhausting the gas in the vacuum reaction chamber 3 to the outside through the gas exhaust ports 32A and 34A. The exhaust means is based on the monitoring result of a pressure gauge (not shown) provided in the vacuum reaction chamber 3. Based on this, the vacuum reaction chamber 3 can be maintained in a vacuum. The pressure in the vacuum reaction chamber 3 is, for example, 1.0 Pa or more and 100 Pa or less.

  The voltage application means 4 includes a state in which the first support 20A is at a higher potential than the second support 20B between the first support 20A and the second support 20B, and the second support 20B is in the first state. This is for applying a pulsed DC voltage so as to alternately repeat a state where the potential is higher than that of the support 20A. More specifically, the voltage application unit 4 sets the second support 20B to the ground potential when supplying a pulsed DC voltage to the first support 20A, while the second support 20B When the pulsed DC voltage is supplied, the first support 20A is set to the ground potential. The voltage applying means 4 includes a DC power supply 40, changeover switches 41 and 42, and terminals 43, 44, 45, and 46.

  The DC power source 40 is for applying a DC voltage to the first and second supports 20A and 20B via the conductive plates 24A and 24B and the conductive columns 22A and 22B.

  The changeover switches 41 and 42 select a state where one of the first and second supports 20A and 20B can be supplied with a voltage from the DC power supply 40, and ground the other support 20A and 20B. Is for selecting. The changeover switch 41 is connected to either the terminal 43 or the terminal 44, and the changeover switch 42 is connected to either the terminal 45 or the terminal 46.

  The terminals 43 to 46 are selectively connected to the changeover switches 41 and 42, and are connected to the conductive plates 24A and 24B via wiring.

  The voltage application means 4 is configured to always ground the other support 20A, 20B when supplying a pulsed DC voltage to one of the first support 20A and the second support 20B. There is no need to do this, and a configuration including a reference power supply different from the DC power supply 40 may be used. In this case, the reference voltage in the reference power source is, for example, −1500 V or more when a negative pulse voltage (see FIG. 5) is applied to the first and second supports 20A and 20B (cylindrical base body 10). When a positive pulse voltage (see FIG. 6) is applied to the first and second supports 20A and 20B (cylindrical base body 10), the voltage is set to, for example, −1500 V or more and 1500 V or less. .

  As shown in FIG. 4, the rotating means 5 is for rotating the first and second support bodies 20 </ b> A and 20 </ b> B, and includes a rotation motor 50 and a rotational force transmission mechanism 51. When the first and second supports 20A and 20B supported by the cylindrical base 20 by the rotating means 5 are rotated, the cylindrical base 10 is rotated together with the first and second supports 20A and 20B. Therefore, it is possible to deposit the decomposition components of the source gas evenly on the outer periphery of the cylindrical substrate 10.

  The rotation motor 50 applies a rotational force to the cylindrical base 10. The operation of the rotary motor 50 is controlled so as to rotate the cylindrical substrate 10 at 1 rpm or more and 10 rpm or less, for example. Various known motors can be used as the rotary motor 50.

  The rotational force transmission mechanism 51 is for transmitting and inputting the rotational force from the rotary motor 50 to the cylindrical base 10, and includes a rotation introduction terminal 52, an insulating shaft member 53, and an insulating flat plate 54.

  The rotation introducing terminal 52 is for transmitting a rotational force while maintaining a vacuum in the vacuum reaction chamber 3. As such a rotation introduction terminal 52, a vacuum seal means such as an oil seal or a mechanical seal can be used by configuring the rotation shaft as a double structure or a triple structure.

  The insulating shaft member 53 and the insulating flat plate 54 maintain the insulation state between the first and second support bodies 20A, 20B and the plate 31, and apply the rotational force from the rotary motor 50 to the first and second support bodies 20A. , 20B. Such an insulating shaft member 53 is formed of an insulating material similar to that of the insulating member 34, for example. Here, the outer diameter D1 of the insulating shaft member 53 is set to be smaller than the outer diameter (the inner diameter of the upper dummy base 29 described later) D2 of the first and second supports 20A and 20B during film formation. ing. More specifically, when the temperature of the cylindrical substrate 10 at the time of film formation is set to 200 ° C. or more and 400 ° C. or less, the outer diameter D1 of the insulating shaft member 53 is such that the first and second supports 20A and 20B have the outer diameter D1. The outer diameter (the inner diameter of the upper dummy base 29 described later) D2 is set to be 0.1 mm or more and 5 mm or less, preferably about 3 mm. In order to satisfy this condition, the outer diameter D1 of the insulating shaft member 53 and the outer diameters of the first and second supports 20A and 20B during non-film formation (in a normal temperature environment (for example, 10 ° C. or higher and 40 ° C. or lower)). The difference from (the inner diameter of the upper dummy base 29 described later) D2 is set to 0.6 mm or more and 5.5 mm or less.

  The insulating flat plate 54 is for preventing foreign matters such as dust and dust falling from above when the plate 31 is attached and detached from adhering to the cylindrical substrate 10 and the deposited film. The insulating flat plate 54 is formed in a disk shape having an outer diameter D3 larger than the inner diameter D2 of the upper dummy base 29. The diameter D3 of the insulating flat plate 54 is 1.5 to 3.0 times the diameter D2 of the cylindrical substrate 10. For example, when the cylindrical substrate 10 having a diameter D2 of 30 mm is used, the insulating flat plate 54 is used. The diameter D3 is about 50 mm.

  When such an insulating flat plate 54 is provided, it is possible to suppress abnormal discharge caused by foreign matter attached to the cylindrical substrate 10, and thus it is possible to suppress the occurrence of film formation defects. Thereby, the yield at the time of forming the electrophotographic photosensitive member 1 can be improved, and the occurrence of image defects when the image is formed using the electrophotographic photosensitive member 1 can be suppressed.

As shown in FIG. 2, the source gas supply means 6 includes a plurality of source gas tanks 60, 61, 62, 63, a plurality of pipes 60A, 61A, 62A, 63A, valves 60B, 61B, 62B, 63B, 60C, 61C. , 62C, 63C, and a plurality of mass flow controllers 60D, 61D, 62D, 63D, which are connected to the gas blowing section 30 via the pipe 64 and the gas inlet 45. Each of the source gas tanks 60 to 63 is filled with, for example, B ₂ H ₆ , H ₂ (or He), CH _4, or SiH ₄ . The valves 60 </ b> B to 63 </ b> B, 60 </ b> C to 63 </ b> C and the mass flow controllers 60 </ b> D to 63 </ b> D are for adjusting the flow rate, composition, and gas pressure of each raw material gas component introduced into the vacuum reaction chamber 3. Of course, in the source gas supply means 6, the type of gas to be filled in each source gas tank 60-63 or the number of source tanks 60-63 depends on the type or composition of the film to be formed on the cylindrical substrate 10. What is necessary is just to select suitably according to.

  Next, a method for forming a deposited film using the plasma CVD apparatus 2 will be described taking as an example the case where the electrophotographic photosensitive member 1 (see FIG. 1) in which an a-Si film is formed on the cylindrical substrate 10 is manufactured.

  First, in forming a deposited film (a-Si film) on the cylindrical substrate 10, the plurality of cylindrical substrates 10 (two in the drawing) were supported after the plate 31 of the plasma CVD apparatus 2 was removed. The first and second supports 20A and 20B are set inside the vacuum reaction chamber 3, and the plate 31 is attached again.

  In supporting the two cylindrical bases 10 with respect to the first and second supports 20A and 20B, on the flanges 21A and 21B, the main parts of the first and second supports 20A and 20B are covered. The dummy substrate 27, the cylindrical substrate 10, the intermediate dummy substrate 28, the cylindrical substrate 10, and the upper dummy substrate 29 are sequentially stacked.

  As each of the dummy bases 27 to 29, a conductive or insulative base whose surface has been subjected to a conductive treatment is selected depending on the use of the product. Usually, a cylinder made of the same material as the cylindrical base 10 is used. What was formed in the shape is used.

  Here, the lower dummy base 27 is for adjusting the height position of the cylindrical base 10. The intermediate dummy base 28 is for suppressing the occurrence of film formation defects due to arc discharge generated between the end portions of the adjacent cylindrical bases 10. The intermediate dummy substrate 28 has a minimum length (1 cm in the present embodiment) that can prevent arc discharge, and the surface side corner portion has a curvature of 0.5 mm or more by curved surface processing or an end surface. A part chamfered so that the length in the axial direction and the length in the depth direction of the part cut by processing is 0.5 mm or more is used. The upper dummy substrate 29 prevents the deposition film from being formed on the first and second supports 20A and 20B, and causes the occurrence of film formation defects due to the peeling of the film formation body once deposited during film formation. It is for suppressing. A part of the upper dummy base 29 protrudes above the first and second supports 20A and 20B.

  Next, the vacuum reaction chamber 3 is hermetically sealed, and the rotating substrate 5 rotates the cylindrical substrate 10 via the first and second supports 20A and 20B, and the cylindrical substrate 10 is heated to exhaust means (not shown). ) To reduce the pressure in the vacuum reaction chamber 3.

  The cylindrical base 10 is heated, for example, by supplying power from the outside to the heaters 26A and 26B to cause the heaters 26A and 26B to generate heat. Due to the heat generated by the heaters 26A and 26B, the cylindrical substrate 10 is heated to a target temperature. The temperature of the cylindrical substrate 10 is selected depending on the type and composition of the film to be formed on the surface thereof. For example, when forming an a-Si film, the temperature is set in the range of 250 ° C. or more and 300 ° C. or less, and the heater 26A. , 26B are kept substantially constant by turning them on and off.

  On the other hand, the vacuum reaction chamber 3 is decompressed by exhausting gas from the vacuum reaction chamber 3 through the gas discharge ports 32A and 34A by an exhaust means (not shown). The degree of pressure reduction in the vacuum reaction chamber 3 is, for example, about 10 Pa. Such a vacuum state can be maintained by controlling the operation of the exhaust unit based on the result of monitoring the pressure in the vacuum reaction chamber 3 with a pressure gauge (not shown).

  Next, when the temperature of the cylindrical substrate 10 reaches a desired temperature and the pressure in the vacuum reaction chamber 3 reaches a desired pressure, the source gas is supplied to the vacuum reaction chamber 3 by the source gas supply means 6 and the first support is provided. A pulsed DC voltage is applied between the body 20A and the second support 20B. As a result, glow discharge occurs between the first support 20A and the second support 20B (cylindrical substrate 10), the source gas component is decomposed, and the decomposed component of the source gas is deposited on the surface of the cylindrical substrate 10. Is done.

  On the other hand, in the exhaust means (not shown), the gas pressure in the vacuum reaction chamber 3 is maintained within the target range while monitoring the pressure gauge (not shown) in the vacuum reaction chamber 3. That is, the inside of the vacuum reaction chamber 3 is maintained at a stable gas pressure by the mass flow controllers 60D to 63D and the exhaust unit in the source gas supply unit 6. The gas pressure in the vacuum reaction chamber 3 is, for example, 1.0 Pa or more and 100 Pa or less.

  The supply of the source gas to the vacuum reaction chamber 3 is performed by controlling the mass flow controllers 60D to 63D while appropriately controlling the open / closed state of the valves 60B to 63B and 60C to 63C, This is carried out by introducing the gas composition into the gas blowing section 30 through the pipes 60A to 63A, 64 and the gas introduction port 35 at a desired composition and flow rate. The source gas introduced into the gas blowing unit 30 is blown out toward the cylindrical substrate 10 through the plurality of gas blowing holes 36. Then, the charge injection blocking layer 11, the photoconductive layer 12, and the surface protective layer are formed on the surface of the cylindrical substrate 10 by appropriately switching the composition of the source gas by the valves 60B to 63B, 60C to 63C and the mass flow controllers 60D to 63D. 13 are sequentially stacked.

  Application of a pulsed DC voltage between the first support 20A and the second support 20B is performed by the voltage applying means 4.

  In general, when high-frequency power over the 13.56 MHz RF band is used, ion species generated in the space are accelerated by the electric field and attracted in the direction according to the positive / negative polarity. Since the electric field is continuously reversed, since the electric field is reversed before the ion species reaches the cylindrical substrate 10 or the discharge electrode, collision of ions with the substrate is reduced. Recombination is repeated in the space, and exhausted again as a gas or a silicon compound such as polysilicon powder.

  On the other hand, a pulsating DC voltage is applied so that the cylindrical substrate 10 has a positive or negative polarity to accelerate the cations to collide with the cylindrical substrate 10, and the impact causes fine irregularities on the surface. When the a-Si film is formed while sputtering, a-Si having a surface with very little unevenness can be obtained. The inventors named this phenomenon the “ion sputtering effect”.

  In such a plasma CVD method, in order to obtain an ion sputtering effect efficiently, it is necessary to apply a power that is faster than the diffusion rate of ions and avoids the polarity reversing continuously. The polarity of the film can be freely adjusted in consideration of the film formation rate determined by the density of the ion species and the polarity of the deposited species depending on the type of the source gas.

  Here, in order to obtain an ion sputtering effect efficiently with a pulsed voltage, the potential difference between the first support 20A and the second support 20B is, for example, in the range of 50 V to 3000 V in absolute value, In consideration of the film formation rate, the absolute value is preferably in the range of 500 V to 3000 V.

  More specifically, when the voltage application means 4 is grounded, the first and second switches 41 and 42 are switched, and the terminals 43 to 46 connected to the change-over switches 41 and 42 are appropriately selected. A negative pulsed DC potential V1 within a range of −3000V to −50V is supplied to one of the support 20A (conductive support 22A) and the second support 20B (conductive support 22B) (see FIG. 5). ) Or a positive pulsed DC potential V1 in the range of 50V to 3000V (see FIG. 6). At this time, of the first support 20A (conductive support 22A) and the second support 20B (conductive support 22B), the supports 20A and 20B to which no DC voltage is applied from the DC power supply 40 are set to the ground potential. The

  On the other hand, when the voltage application means 4 is provided with a reference power supply, a pulse shape is supplied to one of the first support 20A (conductive column 22A) and the second support 20B (conductive column 22B). The DC potential V1 is a value (ΔV−V2) obtained by subtracting the potential V2 supplied from the reference power source from the target potential difference ΔV. The potential V2 supplied from the reference power source is −1500 V or more and 1500 V or less when a negative pulse voltage (see FIG. 5) is applied to the first and second supports 20A and 20B (cylindrical base body 10). When a positive pulse voltage (see FIG. 6) is applied to the first and second supports 20A and 20B (cylindrical base body 10), the voltage is set to −1500 V or more and 1500 V or less.

  The voltage application means 4 further includes a state in which the first support 20A has a higher potential than the second support 20B between the first support 20A and the second support 20B, and the second support 20B A pulsed DC voltage is applied so as to alternately repeat a state where the potential is higher than that of one support 20A. Therefore, the potential applied to the first and second support bodies 20A is obtained by repeating a pulsed DC voltage at regular intervals, and between the first support body 20A and the second support body 20B. Then, the phase is shifted by 180 °.

  Here, the frequency (1 / T (sec)) of the pulsed DC voltage applied to the first and second supports 20A and 20B is set to 300 kHz or less, for example (see FIGS. 5 and 6).

  Even if the thickness of the a-Si photoconductive layer 12 obtained by utilizing such an ion sputtering effect is 10 μm or more, the fine irregularities on the surface are small and the smoothness is hardly impaired. Therefore, the surface shape of the surface layer 13 when a-SiC as the surface layer 13 is laminated on the photoconductive layer 12 by about 1 μm can be a smooth surface reflecting the surface shape of the photoconductive layer 12. Become. On the other hand, even when the surface layer 13 is laminated, the surface layer 13 can be formed as a smooth film with small fine irregularities by utilizing the ion sputtering effect.

  Here, in forming the charge injection blocking layer 11, the photoconductive layer 12, and the surface layer 13, the mass flow controllers 60D to 63D and the valves 60B to 63B and 60C to 63C in the raw material gas supply means 6 are controlled to have a target composition. The source gas is supplied to the vacuum reaction chamber 3 as described above.

For example, when the charge injection blocking layer 11 is formed as an a-Si-based deposited film, as a source gas, a Si-containing gas such as SiH ₄ (silane gas), a dopant-containing gas such as B ₂ H ₆ , and hydrogen ( A mixed gas of diluent gas such as H ₂ ) or helium (He) is used. As the dopant-containing gas, in addition to the boron (B) -containing gas, a nitrogen (N) or oxygen (O) -containing gas can also be used.

When the photoconductive layer 12 is formed as an a-Si-based deposited film, a mixture of a Si-containing gas such as SiH ₄ (silane gas) and a dilution gas such as hydrogen (H ₂ ) or helium (He) is used as a source gas. Gas is used. In the photoconductive layer 12, hydrogen gas is used as a diluting gas so that hydrogen (H) and halogen elements (F, Cl) are contained in the film at 1 atom% or more and 40 atom% or less for dangling bond termination, Alternatively, a halogen compound may be included in the source gas. In addition, the source gas includes a periodic group 13 element (hereinafter referred to as “Group 13 element”) in order to obtain desired characteristics such as electrical characteristics such as dark conductivity and photoconductivity and optical band gap. Or a group 15 element of the periodic table (hereinafter abbreviated as “Group 15 element”), and elements such as carbon (C) and oxygen (O) are included to adjust the above characteristics. You may let them.

  The group 13 element and the group 15 element are desirable in that boron (B) and phosphorus (P) are excellent in covalent bonding and can change the semiconductor characteristics sensitively, and that excellent photosensitivity can be obtained. . When the group 13 element and the group 15 element are contained together with elements such as carbon (C) and oxygen (O) in the charge injection blocking layer 11, the content of the group 13 element is 0.1 ppm or more and 20000 ppm. Hereinafter, the content of the Group 15 element is adjusted to be 0.1 ppm or more and 10,000 ppm or less. Further, when the group 13 element and the group 15 element are contained in the photoconductive layer 12 together with elements such as carbon (C) and oxygen (O), or the charge injection blocking layer 11 and the photoconductive layer 12 When elements such as carbon (C) and oxygen (O) are not included, the group 13 element is adjusted to 0.01 ppm to 200 ppm, and the group 15 element is adjusted to 0.01 ppm to 100 ppm. . In addition, by changing the content of the Group 13 element or the Group 15 element in the source gas with time, the concentration of these elements may be provided with a gradient over the layer thickness direction. In this case, the content of the Group 13 element and the Group 15 element in the photoconductive layer 12 may be such that the average content in the entire photoconductive layer 12 is within the above range.

  The photoconductive layer 12 may contain microcrystalline silicon (μc-Si) in the a-Si material. When μc-Si is included in the photoconductive layer 12, dark conductivity and bright conductivity can be increased, and thus there is an advantage that the degree of freedom in designing the photoconductive layer 12 is increased. Such μc-Si can be formed by adopting the film formation method described above and changing the film formation conditions. For example, in the glow discharge decomposition method, it can be formed by setting the temperature and DC pulse power of the cylindrical substrate 10 to be high and increasing the flow rate of hydrogen as a dilution gas. Further, in the photoconductive layer 12 containing μc-Si, the same elements as described above (Group 13 element, Group 15 element, carbon (C), oxygen (O), etc.) may be added. Good.

When the surface layer 13 is formed as an a-SiC-based deposited film, a mixed gas of a Si-containing gas such as SiH ₄ (silane gas) and a C-containing gas such as CH ₄ is supplied as a source gas. The composition ratio of Si and C in the source gas may be changed continuously or intermittently. That is, as the C ratio increases, the film formation rate tends to be slow. Therefore, the C ratio is low for the portion close to the photoconductive layer 12 in the surface layer 13, while the C ratio is high for the free surface side. The surface layer 13 may be formed as described above. For example, on the photoconductive layer 12 side (interface side) of the surface layer 13, the x value (carbon ratio) in hydrogenated amorphous silicon carbide (a-Si _1-x C _x : H) exceeds 0 to 0. After depositing a first SiC layer having a relatively high Si composition ratio of less than 8, a second SiC layer having a C concentration increased to an x value (carbon ratio) of about 0.95 or more and less than 1.0 was deposited. A two-layer structure may be used.

  The film thickness of the first SiC layer is determined from the breakdown voltage, the residual potential, the film strength, etc., and is usually 0.1 μm or more and 2.0 μm or less, preferably 0.2 μm or more and 1.0 μm or less, and optimally 0. .3 μm or more and 0.8 μm or less. The film thickness of the second SiC layer is determined from pressure resistance, residual potential, film strength, life (wear resistance), etc., and is usually 0.01 μm or more and 2 μm or less, preferably 0.02 μm or more and 1.0 μm or less. Optimally, the thickness is 0.05 μm or more and 0.8 μm or less.

The surface layer 13 can also be formed as an aC layer as described above. In this case, a C-containing gas such as C ₂ H ₂ (acetylene gas) or CH ₄ (methane gas) is used as the source gas. The thickness of the surface layer 13 is usually 0.1 μm or more and 2.0 μm or less, preferably 0.2 μm or more and 1.0 μm or less, and most preferably 0.3 μm or more and 0.8 μm or less.

  When the surface layer 13 is formed as an aC layer, since the binding energy of the C—O bond is smaller than that of the Si—O bond, the surface layer 13 is formed of an a—Si based material. Further, it is possible to more reliably suppress the surface layer 13 from being oxidized. Therefore, when the surface layer 13 is formed as an aC layer, the surface layer 13 is appropriately prevented from being oxidized by ozone generated by corona discharge during printing. It is possible to suppress the occurrence of image flow under the environment.

When film formation on the cylindrical substrate 10 is completed, the electrophotographic photosensitive member 1 shown in FIG. 1 can be obtained by extracting the cylindrical substrate 10 from the first and second supports 20A and 20B. After the film formation, in order to remove the film formation residue, each member in the vacuum reaction chamber 3 is disassembled and washed with acid, alkali, blast, etc., so that there is no dust generation that causes a defect during the next film formation. Wet etching is performed. Instead of wet etching, it is also effective to perform gas etching using a halogen-based gas (ClF ₃ , CF ₄ , O ₂ , NF ₃ , SiF ₆ or a mixed gas thereof).

  According to the present invention, since film formation is performed using the ion sputtering effect, arc discharge during film formation is suppressed without reducing the film formation rate, and a good deposited film (charge injection prevention) with less characteristic unevenness and defects is suppressed. Layer 11, photoconductive layer 12 and surface layer 13) can be formed at high speed. Therefore, it is possible to efficiently provide the electrophotographic photosensitive member 1 having a high quality deposited film with little film thickness unevenness. Therefore, when image formation is performed using the electrophotographic photosensitive member 1 manufactured according to the present invention, image characteristics can be improved by suppressing the occurrence of image defects such as the occurrence of black spots.

  In the present invention, the first support 20A has a higher potential than the second support 20B relative to the first and second supports 20A and 20B, and the second support 20B is in the first support 20A. A pulsed DC voltage is applied so as to alternately repeat the state of higher potential. Therefore, it is possible to form a deposited film with more efficiency and less unevenness. That is, if a pulsed DC voltage is applied between the first support 20A and the second support 20B, the cations generated by the plasma discharge at the time of voltage application are the first support 20A and the second support. Acceleration is performed between the body 20B and the cylindrical base 10 supported by these supports 20A and 20B. Then, if the application of a pulsed DC voltage between the first support 20A and the second support 20B is alternately performed between the first support 20A and the second support 20B, this can be achieved. Cations can be accelerated while the electric field is inverted between the supports 20A and 20B. As a result, since cations can be effectively present in the region between the first support 20A and the second support 20B, the accelerated cations can efficiently collide with the cylindrical substrate 10. it can. As a result, in the present invention, it is possible to obtain a deposited film having a surface with very little unevenness, and to improve the deposition rate.

  Moreover, if the cation produced | generated by discharge can exist effectively between 20 A of 1st support bodies and the 2nd support body 20B, compared with the case where discharge is caused between the gas blowing part 30 and a support body. The cations generated by the discharge can be efficiently attached to the first and second supports 20A and 20B, and a large distance between the gas blowing portion 30 and the support can be secured. As a result, it is possible to prevent cations from adhering to the gas blowing portion 30 and the like to form an unnecessary film. This facilitates cleaning of components such as the gas blowing unit 30 in the apparatus 2, shortens the time required for producing one electrophotographic photosensitive member 1, and improves productivity.

  Next, a second embodiment of the present invention will be described with reference to FIGS. Note that “+” or “−” in FIGS. 8A and 8B indicates that the first and second supports 20A ′ and 20B ′ are “high potential” relative to the other support. Alternatively, it means “low potential” and does not necessarily indicate polarity.

  The inter-deposition forming apparatus 2 ′ shown in FIG. 7 includes a plurality of first supports 20A ′ and a plurality of second supports 20B ′, and the same number (three in the drawing) are provided. ing. The plurality of first and second supports 20A ′ and 20B ′ are alternately arranged on the same circumference. The first and second supports 20A 'and 20B' are alternately pulsed DC voltage (Fig. 5 and Fig. 5) between the first support 20A 'and the second support 20B' by voltage applying means (not shown). (See FIG. 6). That is, as shown in FIG. 8A, the first support 20A ′ is at a higher potential than the second support 20B, and as shown in FIG. 8B, the second support 20B ′. Are alternately set at a higher potential than the first support 20A ′. As a result, a pulsed DC voltage is repeatedly applied at regular intervals between the first support 20A ′ and the second support 20B ′ as shown in FIG. 5 or FIG. Between the first support 20A ′ and the second support 20B ′, the phase of the continuous pulse waveform is shifted by 180 °.

  Here, in order to efficiently obtain the ion sputtering effect by the pulse voltage, the potential difference between the first support 20A ′ and the second support 20B ′ is, for example, in the range of 50 V or more and 3000 V or less in absolute value. In consideration of the film formation rate, the absolute value is preferably in the range of 500 V or more and 3000 V or less. Further, the frequency of the pulsed DC voltage applied to the first and second supports 20A ′ and 20B ′ is set to 300 kHz or less, for example (see FIGS. 5 and 6).

  In such a deposited film forming apparatus 2 ′, a plurality of first and second supports 20A ′ and 20B ′ are alternately arranged on the same circumference, and the first support 20A ′ is the second support. A pulsed DC voltage is applied so that a state where the potential is higher than that of the body 20B ′ and a state where the second support 20B ′ is higher than the first support 20A ′ are alternately repeated. Therefore, the first support 20A ′ (or the second support 20B ′) generates glow discharge between two adjacent second supports 20B ′ (first support 20A ′) and supports them. The cations generated by the glow discharge move between the bodies 20A ′ and 20B ′. As a result, the deposited film forming apparatus 2 ′ can efficiently obtain a deposited film having a surface with extremely few irregularities, and improve the productivity due to the improvement of the film formation rate and the ease of cleaning. Can do.

  Next, a third embodiment of the present invention will be described with reference to FIG. 9 and FIG. 10A and 10B, “+” and “−” indicate that the first and second supports 20A ″ and 20B ″ are “high potential” and “low” with respect to the other support. It means “potential” and does not necessarily indicate polarity.

  The inter-deposition forming apparatus 2 ″ shown in FIG. 9 includes a plurality of first supports 20A ″ and a plurality of second supports 20B ″, and the same number (12 on the drawing) is provided. The plurality of first supports 20A ″ are arranged concentrically, and the plurality of second supports 20B ″ are also arranged concentrically. The arrangement center of the plurality of first supports 20A ″ and the plurality of first supports 20A ″ are arranged concentrically. The arrangement centers of the two support bodies 20B ″ coincide with or substantially coincide with each other, and the plurality of first support bodies 20A ″ are arranged so as to surround the plurality of second support bodies 20B ″. The second supports 20A ″ and 20B ″ are arranged in a staggered manner in the circumferential direction.

  The first and second supports 20A "and 20B" are alternately pulsed DC voltage between the first support 20A "and the second support 20B" by a voltage applying means (not shown) (see Figs. 5 and 5). 6) can be applied. That is, as shown in FIG. 10A, the first support 20A ″ has a higher potential than the second support 20B ″, and as shown in FIG. 10B, the second support 20B. The state in which “is higher than the potential of the first support 20A” is alternately achieved. As a result, a pulsed DC voltage is repeatedly applied at regular intervals between the first support 20A ″ and the second support 20B ″ as shown in FIG. 5 or FIG. Between the first support 20A ″ and the second support 20B ″, the phase of the continuous pulse waveform is shifted by 180 °.

  Here, in order to obtain an ion sputtering effect efficiently with a pulsed voltage, the potential difference between the first support 20A ″ and the second support 20B ″ is, for example, in the range of 50 V or more and 3000 V or less in absolute value. In consideration of the film formation rate, the absolute value is preferably in the range of 500 V or more and 3000 V or less. Further, the frequency of the pulsed DC voltage applied to the first and second supports 20A ″ and 20B ″ is set to 300 kHz or less, for example (see FIGS. 5 and 6).

  In such a deposited film forming apparatus 2 ″, the plurality of first and second supports 20A ″ and 20B ″ are arranged in the circumferential direction so that the plurality of first supports 20A ″ surround the plurality of second supports 20B ″. On the other hand, the first support 20A ″ is at a higher potential than the second support 20B ″ between the first support 20A ″ and the second support 20B ″. The pulsed DC voltage is applied so that the second support 20B ″ and the state where the second support 20B ″ is at a higher potential than the first support 20A ″ are alternately repeated. Therefore, the first support 20A ″ ( Alternatively, the second support 20B ″) generates a glow discharge between two adjacent second supports 20B ″ (first support 20A ″), and between the supports 20A ″ and 20B ″. Cations generated by glow discharge move As a result, in the deposited film forming apparatus 2 ″, it is possible to efficiently obtain a deposited film having a surface with very little unevenness, and to improve the productivity due to the improvement of the film forming rate and the ease of cleaning. be able to.

It is sectional drawing which shows an example of the electrophotographic photoreceptor used as the manufacture object in this invention, and its principal part enlarged view. 1 is a longitudinal sectional view showing a deposited film forming apparatus according to a first embodiment of the present invention. FIG. 3 is a transverse sectional view showing the deposited film forming apparatus shown in FIG. 2. It is a principal part enlarged view of the deposited film forming apparatus shown in FIG. It is a graph for demonstrating the voltage application state in the deposited film formation apparatus shown in FIG. It is a graph for demonstrating the other voltage application state in the deposited film formation apparatus shown in FIG. It is a cross-sectional view showing a deposited film forming apparatus according to a second embodiment of the present invention. FIG. 8 is a schematic diagram showing a change in potential in the first and second supports when a pulsed DC voltage is alternately applied between the first and second supports in the deposited film forming apparatus shown in FIG. 7. . It is a cross-sectional view showing a deposited film forming apparatus according to a third embodiment of the present invention. FIG. 10 is a schematic diagram showing a change in potential in the first and second supports when a pulsed DC voltage is alternately applied between the first and second supports in the deposited film forming apparatus shown in FIG. 9. .

Explanation of symbols

1 Electrophotographic Photoreceptor 10 Cylindrical Substrate (Deposited Film Formation Object)
2,2 ', 2 "plasma CVD equipment (deposition film forming equipment)
20A, 20A ′, 20A ″ first support (first conductor)
20B, 20B ′, 20B ″ second support (second conductor)
3 Vacuum reaction chamber (reaction chamber)
4 Voltage application means 6 Raw material gas supply means

Claims (20)

A first step of accommodating the deposited film forming object in a reaction chamber in a state where the deposited film forming object is supported by each of the first conductor and the second conductor that are spaced apart from each other;
A second step in which the reaction chamber has a reaction gas atmosphere;
Between the first conductor and the second conductor, the state in which the first conductor has a higher potential than the second conductor and the state in which the second conductor has a higher potential than the first conductor. A third step of applying a pulsed DC voltage so as to repeat alternately;
A method for forming a deposited film, comprising:   In the third step, when the pulsed DC voltage is supplied to the first conductor, the second conductor is set to the ground potential or the reference potential, while the pulsed DC voltage is applied to the second conductor. The deposited film forming method according to claim 1, wherein when the first conductor is supplied, the first conductor is set to a ground potential or a reference potential.   The deposited film forming method according to claim 1, wherein in the third step, a negative pulsed DC voltage is applied between the first conductor and the second conductor.   In the first step, the deposited film is formed in the reaction chamber in a state where one or a plurality of cylindrical conductive substrates as the deposited film forming object are supported on the first conductor and the second conductor, respectively. The deposited film forming method according to claim 1, wherein a formation target is accommodated.   5. The deposited film forming method according to claim 4, wherein, in the first step, a plurality of conductive substrates are arranged side by side in the axial direction of the conductive substrate on each of the first conductor and the second conductor.   6. The deposited film forming method according to claim 4, wherein the cylindrical conductive substrate is an electrophotographic photoreceptor substrate.   The said 1st step WHEREIN: Each of the several 1st conductor arrange | positioned concentrically and the 2nd conductor arrange | positioned concentrically each support the said deposit film formation object of Claim 4 thru | or 6. The deposited film forming method according to any one of the above.   The deposited film forming method according to claim 7, wherein the plurality of first conductors and the plurality of second conductors are alternately arranged in the circumferential direction on the same circumference.   The deposited film forming method according to claim 7, wherein the plurality of first conductors are disposed so as to surround the plurality of second conductors.   The deposited film forming method according to claim 9, wherein the plurality of first conductors and the plurality of second conductors are arranged in a staggered manner in the circumferential direction. A reaction chamber for accommodating a plurality of deposited film formation objects;
One or more first conductors and one or more second conductors that are spaced apart from each other in the reaction chamber and support the plurality of deposited film formation objects;
Gas supply means for supplying a reactive gas into the reaction chamber;
Between the first conductor and the second conductor, the state in which the first conductor has a higher potential than the second conductor and the state in which the second conductor has a higher potential than the first conductor. Voltage application means for applying a pulsed DC voltage to repeat alternately,
A deposited film forming apparatus comprising:   The voltage application means sets the second conductor to a ground potential or a reference potential when supplying a pulsed DC voltage to the first conductor, while the pulse applying DC voltage to the second conductor. The deposited film forming apparatus according to claim 11, wherein the first conductor is configured to have a ground potential or a reference potential when supplying the first conductor.   The deposited film forming apparatus according to claim 11, wherein the voltage applying unit is configured to apply a negative pulsed DC voltage between the first conductor and the second conductor.   Each of the said 1st conductor and the said 2nd conductor is comprised so that the 1 or several cylindrical conductive base | substrate as said deposited film formation target object can be supported. The deposited film forming apparatus described.   The deposited film formation according to claim 14, wherein each of the first conductor and the second conductor is configured such that the plurality of cylindrical conductive substrates can be arranged side by side in the axial direction of the conductive substrate. apparatus.   The deposited film forming apparatus according to claim 14 or 15, wherein the cylindrical conductive substrate is a substrate for an electrophotographic photosensitive member.   The deposited film forming apparatus according to claim 14, wherein a plurality of first conductors and a plurality of second conductors are concentrically arranged in the reaction chamber.   The deposited film forming apparatus according to claim 17, wherein the plurality of first conductors and the plurality of second conductors are alternately arranged in the circumferential direction on the same circumference.   The deposited film forming apparatus according to claim 17, wherein the plurality of first conductors are disposed so as to surround the plurality of second conductors. The deposited film forming apparatus according to claim 19, wherein the plurality of first conductors and the plurality of second conductors are arranged in a staggered manner in the circumferential direction.

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