JP3402952B2 - Method and apparatus for forming deposited film - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention is useful for electrophotographic photosensitive devices as semiconductor devices, image input line sensors, imaging devices, photovoltaic devices, and the like.
The present invention relates to a deposited film forming method and apparatus by plasma CVD capable of favorably forming a non-single crystalline functional deposited film.

[0002]

2. Description of the Related Art There are various methods for plasma processing apparatuses used in semiconductors and the like, depending on their respective applications. For example, in the formation of a deposited film, an amorphous silicon semiconductor film is used as a photoconductor for electrophotography, which uses a plasma CVD method with high frequency power, and an apparatus and method that make use of its characteristics are used. The demand for is increasing, and various studies are being made.

For example, in Japanese Patent Laid-Open No. 63-14875, the length (L) of the cathode electrode and the distance (d) from the anode electrode to the cathode electrode are set to 5 ≦ L / d ≦ 40 so that they are stable and uniform. A technique is disclosed in which plasma discharge is obtained and the film uniformity and film quality are improved.

Further, in Japanese Patent Publication No. 62-37111, high frequency power is applied to the electrode surface facing the discharge surface in an amount of 0.
A technique is disclosed in which an amorphous silicon film having high sensitivity and high resistance can be obtained by setting the total gas flow rate to 3 Wcm ² or more and the total gas flow rate to 0.01 min ^-1 or more with respect to the internal volume of the discharge chamber.

These techniques have improved the electrical, optical and photoconductive characteristics of the electrophotographic photoconductor and the use environment characteristics, and the image quality has been improved accordingly.

On the other hand, when a copying machine is used in an office in recent years, space-saving due to miniaturization is progressing, and accordingly, electrophotographic photoconductors are also required to be miniaturized. Further, since the frequency of use of printers has increased in recent years, demand for amorphous silicon photoconductors having a diameter smaller than that of electrophotographic photoconductors having a diameter of about 80 mm which have been conventionally used in copying machines is also increasing. Therefore, when an amorphous silicon photoconductor having a diameter of about 40 mm, which is smaller than the conventional one, was manufactured as a photoconductor for electrophotography, it was found that the following phenomenon different from the conventional case may occur. did.

That is, it has been found that the electrophotographic photosensitive member having a smaller diameter than that of the conventional one has a tendency that the temperature of the cylindrical substrate surface rises rapidly during the film formation, so that the film is easily distorted and the film is easily peeled off.
If film peeling occurs in the produced electrophotographic photoconductor, it cannot be used as an electrophotographic photoconductor and productivity is greatly reduced, which causes a cost increase.

Further, the film quality of the deposited film in the direction of the generatrix is apt to be distributed, and it appears as a phenomenon such as density unevenness, sensitivity unevenness, and image roughness in the electrophotographic photoreceptor. In recent years, as the performance of copiers has advanced and digital and color machines have become widespread, electrophotographic photoreceptors are required to have higher image quality and quality than ever before. Since the characteristics of the deposited film are required, it is important to reduce the distribution of the quality of the deposited film and improve the characteristics of the deposited film.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce film peeling when producing an electrophotographic photosensitive member having a smaller diameter than before, and to improve the film quality of the deposited film in the generatrix direction. It is an object of the present invention to provide a deposited film forming method and apparatus capable of manufacturing a good electrophotographic photosensitive member which has a reduced distribution and is free from density unevenness, sensitivity unevenness, and image roughness.

[0010]

The above object can be achieved by the following means.

That is, according to the present invention, a substrate heating heater is fixed in a vacuum-tight deposition chamber equipped with an evacuation means and a source gas supply means, and the substrate heating heater is included.
A cylindrical base substrate having a diameter of 45 mm or less, to which an auxiliary substrate also serving as a discharge electrode is attached, is rotatably installed, and high-frequency power is applied between the cylindrical substrate and the cathode electrode which is provided on the same axis as the outer casing. In the coaxial type deposition film forming method or apparatus by the plasma CVD method for generating a glow discharge to form a deposition film containing silicon on the cylindrical substrate, the cylindrical substrate facing the glow discharge surface is formed. When the surface area is Sl, the surface area of the cathode electrode is S2, the electric power applied to the cathode electrode is P, and the SiH4 gas flow rate is f, the following formula A and formula 5W≤P / (S2 / S1) ≤70W ... (A) 5 × 10 ^-3 W / sccm ≦ P / (f · S ₂ / S1) ≦ 7 × 10 ^-1 W / sccm (B) With And forming a photoreceptive member composed of at least two layers of a photoconductive layer and a surface protective layer on the cylindrical substrate, a lower blocking layer, a photoconductive layer, and a surface protective layer on the cylindrical substrate. Forming a light receiving member composed of at least three layers.

Further, according to the present invention, a substrate heating heater is fixed in a vacuum-tight deposition chamber provided with an exhaust means and a source gas supply means, and an auxiliary substrate also serving as a discharge electrode is included so as to include the substrate heating heater. The mounted cylindrical substrate having a diameter of 45 mm or less is rotatably installed, and high-frequency power is applied between the cylindrical substrate and a cathode electrode which is provided on the same axis and which is provided on the same axis. In a coaxial type deposited film forming apparatus by a plasma CVD method for forming a deposited film containing silicon on the cylindrical substrate, the surface area (S) of the cylindrical substrate facing the glow discharge surface
The ratio of the surface area (S2) of the cathode electrode with respect to 1) and the electric power (P) applied to the cathode electrode are set so as to satisfy the following expression A, and 5 W ≦ P / (S2 / S1) ≦ 70 W ... (A) In addition, the SiH4 gas flow rate (f) introduced into the deposition chamber is set to satisfy the following formula B: 5 × 10 ⁻³ W / scccm ≦ P / (f · S2 / S1) ≦ 7 × 10 ⁻¹ W / scc m ... (B) The present invention proposes a deposited film forming apparatus characterized by being set, and comprising at least two layers of a photoconductive layer and a surface protective layer on the cylindrical substrate. Forming a light-receiving member, and forming a light-receiving member composed of at least three layers of a lower blocking layer, a photoconductive layer and a surface protective layer on the cylindrical substrate.

[0013]

The present invention will be described in more detail below.

When an amorphous silicon photoconductor is manufactured by glow discharge using a conventional cylindrical substrate having a diameter of 108 mm and 80 mm, the phenomenon that the surface temperature of the cylindrical substrate rapidly rises during film formation is almost always observed. Did not happen. However, when an amorphous silicon photoconductor is manufactured by glow discharge using a cylindrical substrate having a diameter of 45 mm or less, the temperature of the cylindrical substrate surface rises rapidly during film formation, and the film is easily distorted. It was found that the phenomenon of peeling occurred. Therefore, the present inventor has made diligent studies by paying attention to various densities of electric power applied to the cathode electrode, which are considered as parameters involved in the increase in the surface temperature of the cylindrical substrate due to discharge. As a result, the ratio of the surface area (S2) of the cathode electrode to the surface area (S1) of the cylindrical substrate facing the glow discharge surface:
The ratio of the power (P) applied to the cathode electrode to S2 / S1, that is, the power density to the surface area ratio of the cylindrical substrate facing the glow discharge surface and the cathode electrode: P / (S
It was found that 2 / Sl) is greatly involved in the increase in the surface temperature of the cylindrical substrate during film formation. That is, P / (S2 / S
It was found that the film peeling was effective by specifying 1).

Further, when an amorphous silicon photoconductor is produced by glow discharge using a cylindrical substrate having a diameter of 45 mm or less, the inventors of the present invention have been concerned with the cause that the distribution of the film quality of the deposited film in the generatrix direction tends to occur. We considered that there was no problem in the manufacturing process of the electrophotographic photosensitive member, and conducted a study focusing on the discharge state. When the emission intensity of plasma was measured, it was found that the emission intensity in the generatrix direction sometimes fluctuated and the plasma state became unstable. The inventors of the present invention considered that the distribution of the film quality might be caused by the influence of the occasional fluctuation of the emission intensity.

Therefore, various studies were conducted on various densities of electric power applied to the cathode electrode and SiH4 gas flow rates, which are considered as parameters affecting the discharge state.
As a result, by specifying the power density: P / (S2 / Sl) with respect to the surface area ratio of the cylindrical substrate facing the glow discharge surface to the SiH4 gas flow rate and the cathode electrode, the emission intensity is occasionally increased in the busbar direction. It was found that the fluctuation was reduced and the film quality distribution of the deposition concentration in the bus line direction was also reduced. As a result, it was found that a good deposited film with improved density unevenness, sensitivity unevenness, and image roughness was obtained.

As described above, the power density with respect to the surface area ratio of the cylindrical substrate facing the glow discharge surface and the cathode electrode: P / (S2 / Sl) and the SiH4 gas flow rate (f), the above glow discharge surface. Power density to surface area ratio of facing cylindrical substrate and cathode electrode: P / (S2
The effect of the present invention can be obtained by specifying the ratio of / Sl: P / (f · S2 / Sl) so as to satisfy the following expressions A and B.

5W ≦ P / (S2 / S1) ≦ 70W− (A) 5 × 10 ^-3 W / sccm ≦ P / (f · S2 / Sl) ≦ 7 × 10 ⁻¹ W / sccm ... (B) Hereinafter, the method and apparatus for forming a deposited film of the present invention will be described in detail with reference to the drawings.

FIG. 1 schematically shows an example of an apparatus used in the method for forming a deposited film of the present invention, which is suitable for forming a deposited film on a cylindrical substrate such as an electrophotographic photoreceptor. It is a thing. In FIG. 1, reference numeral 100 denotes a deposition chamber for forming a deposited film, which is connected to an exhaust device (not shown) via an exhaust port 110. Reference numeral 106 is a raw material gas inlet for introducing the raw material gas into the deposition chamber, and introduces the raw material gas into the deposition chamber from a gas supply system (not shown). Reference numeral 102 denotes a cylindrical base, which is set on the auxiliary base 103 and is held by the rotating shaft 105 at the upper portion. The rotating shaft 105 is rotatably attached to the deposition chamber. Reference numeral 104 denotes a substrate heating heater for heating the cylindrical substrate to a predetermined temperature, which is fixed in the deposition chamber. Cylindrical substrate 102
Is rotated by a drive motor 107 via a rotary shaft 105 to make the film thickness in the circumferential direction uniform. Reference numeral 109 is a high frequency power source for generating a high frequency, and the high frequency output is wired so as to be applied to the cathode electrode 101 via the matching unit 108. As shown in the figure, the cathode electrode 101 may also serve as the inner wall of the deposition chamber 100. In the deposited film forming method of the present invention, the cathode electrode 1 with respect to the surface area (S1) of the cylindrical substrate 104 facing the glow discharge surface.
The ratio of the power (P) applied to the cathode electrode 101 to the ratio of the surface area (S2) of 01: S2 / S1: P / (S2
/ Sl) is preferably 5W ≦ P / (S2 / Sl) ≦ 70W. Outside the above range, the effect of reducing film peeling is small.

FIG. 2 shows another example of the auxiliary substrate 2.
03 except that it is held in the form of hanging from above.
Is the same as. When the auxiliary substrate 203 is hung from above as shown in FIG. 2, the inner surface of the auxiliary substrate 203 is the only heater 204 for heating the substrate, and the space between the auxiliary substrate 203 and the heater 204 for heating the substrate expands. This is suitable because the range of diameter reduction of the cylindrical substrate is widened.

Cylindrical substrates 102 and 202 and auxiliary substrate 1
03 and 203 should just have a material according to the purpose of use. In terms of material, copper, aluminum, gold,
Silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, titanium, and stainless steel are preferable because they have good electric conductivity. Furthermore, a composite material of two or more of these materials is also desirable because it has improved heat resistance.

The materials for the cathode electrodes 101 and 201 are copper, aluminum, gold, silver, platinum, lead, nickel,
Cobalt, iron, chromium, molybdenum, titanium, stainless steel and the like are preferable because they have good thermal conductivity and good electrical conductivity. A composite material of two or more of these materials is also preferably used. Further, the shape is preferably a cylindrical shape for ease of processing, but an elliptical shape or a polygonal shape may be used if necessary.

The cathode electrodes 101 and 201 may be provided with a cooling means if necessary. As a specific cooling means, cooling with water, air, liquid nitrogen, a Peltier element, or the like is used as necessary.

The oscillating frequency of the high-frequency power sources 109 and 209 used is usually 13.56 MHz, which is often preferable, but it is not particularly limited. Further, any output can be suitably used as long as it can generate electric power suitable for the device. Further, the output fluctuation rate of the high frequency power supply may be any value.

The matching units 108 and 208 used can be suitably used in any configuration as long as they can match the high frequency power source and the load. Further, as a method for obtaining matching, an automatically adjusted method is suitable for avoiding complications during manufacturing, but even a manually adjusted method has no influence on the effect of the present invention. . Regarding the position where the matching device is placed, there is no problem wherever it is installed within the range where matching can be achieved, but it is better to place it so that the inductance of the wiring between the matching device and the cathode is as small as possible. It is desirable because it will be possible to match the conditions.

Formation of a deposited film in the apparatus shown in FIG. 1 is performed according to the following procedure.

First, the cylindrical substrate 102 whose surface is mirror-finished by using a lathe is attached to the auxiliary substrate 103, and the deposition chamber 1
It is attached to the rotary shaft 105 in 00.

Next, the inside of the deposition chamber 100 is temporarily evacuated by an exhaust device (not shown) through the exhaust port 110, and then a raw material gas introduction valve (not shown) is opened to supply an inert gas for heating, eg, argon gas, to the raw material gas. From the inlet 106 to the deposition chamber 100
And the flow rate of the heating gas is adjusted so that the inside of the deposition chamber 100 has a desired pressure.
Then, the cylindrical motor 102 is driven by the driving motor 107.
While rotating, the temperature controller (not shown) is operated to heat the cylindrical substrate 102 by the substrate heating heater 104. In the deposited film forming apparatus shown in FIG. 1, the cylindrical substrate is rotatable, but the effect of the present invention is not obtained unless the cylindrical substrate is rotated, and the present invention can be achieved even in a stationary state. The effect of is obtained. When the cylindrical substrate 102 is heated to a desired temperature, a raw material gas introduction valve (not shown) is closed to stop the gas flow into the deposition chamber.

To form the deposited film, a raw material gas introduction valve (not shown) is opened to supply a predetermined raw material gas such as silane gas, hydrogen gas, methane gas, etc. from the raw material gas introduction port 106, and diborane gas, phosphine gas, etc. The doping gas is mixed by a mixing panel (not shown) and then introduced into the deposition chamber 100, and the exhaust speed is adjusted so as to maintain a desired pressure. After the pressure is stabilized, the high frequency power supply 109 causes a frequency of 13.
Power of 56 MHz is supplied to cause glow discharge.
At this time, the matching unit 108 is adjusted so as to minimize the reflected wave. The value obtained by subtracting the reflected power from the high frequency incident power is adjusted to a desired value, the power supply is stopped when the desired film thickness is formed, the flow of the source gas into the deposition chamber 100 is stopped, and the inside of the deposition chamber is temporarily stopped. The vacuum is pulled to complete the formation of the layer. During this period, it is desirable to form the deposited film while rotating the cylindrical substrate in order to equalize the film thickness in the circumferential direction. When stacking deposited films having various functions, the above operation is repeated. When the apparatus of FIG. 2 is used, the deposited film may be formed similarly to the case of using the apparatus of FIG. When the a-Si: H film is formed in the present invention, the above P / (S) with respect to the SiH4 gas flow rate (f) is used.
2 / S1) ratio: P / (f · S2 / Sl) is 5 × ^10-3
W / sccm ≦ P / (f · S2 / Sl) ≦ 7 × 10 ⁻¹ W
/ Sccm is preferable. Outside the above range, the effect of reducing the film quality distribution in the generatrix direction is small.

The effects of the present invention will be specifically described below with reference to experimental examples and examples, but the present invention is not limited to these. (Experimental Example 1) In the deposited film forming apparatus shown in FIG. 1, a high frequency power source 109 having an oscillation frequency of 13.56 MHz was used.
An a-Si: H film was formed on a cylindrical substrate 102 made of aluminum and having a diameter of 45 mm to prepare an electrophotographic photoreceptor. In this experimental example, the surface area (S1) of the aluminum-made cylindrical substrate 102 facing the discharge surface, the surface area of the aluminum-made cylindrical cathode electrode 101 (S2),
Regarding the power (P) applied from the high frequency power source 109 to the cathode electrode 101, P / (S2 / S1) is (a) 3 W,
(B) 5W, (c) 10W, (d) 25W, (e) 50
W, (f) 70 W, (g) 75 W, (h) 400 W were changed to prepare an electrophotographic photoreceptor according to the conditions shown in Table 2. P / (S2 for SiH4 gas flow rate (f)
/ Sl) ratio: P / (f · S2 / S1) is the lower blocking layer,
The photoconductive layer and the surface protective layer are as shown in Table 1 below.

[0031]

[Table 1]

[0032]

Table 2 Lower blocking layer ... SiH4 200 sccm H2 300 sccm NO 8 sccm B2H6 2000 ppm (relative to SiH4) Internal pressure 40 Pa film thickness 1 μm Photoconductive layer ... SiH4 400 sccm H2 800 sccm Internal pressure 53 Pa film thickness 20 μm Surface protection layer ... SiH4 400 sccm CH. 40 Pa Film thickness 0.6 μm (Experimental Example 2) In the deposited film forming apparatus shown in FIG. 2, a high frequency power source 209 with an oscillation frequency of 13.56 MHz was used.
An a-Si: H film was formed on a cylindrical base body 202 made of aluminum and having a diameter of 45 mm to prepare an electrophotographic photoreceptor. In this example, P / (S2 / Sl) = 8 W in Experimental Example 1 was used, and the SiH4 gas flow rates of the lower blocking layer, the photoconductive layer, and the surface protective layer were adjusted to the same flow rate, and the lower blocking layer, the photoconductive layer, and By changing the SiH4 gas flow rate of the surface protection layer, SiH
Ratio of P / (S2 / Sl) to 4 gas flow rate (f): P
/ (F · S2 / S1) is 4 × 10 ⁻³ W / sccm, 5 ×
10 ^-3 W / sccm, 2x10 ^-2 W / sccm, 8xl
0 ^-2 W / sccm, 7x10 ^-1 W / sccm, 8x10
^-1 W / sccm was changed to the same as in Experimental Example 1,
Electrophotographic photoreceptors were prepared according to the conditions shown in Table 2.

The electrophotographic photoreceptors produced in Experimental Examples 1 and 2 were evaluated by the following methods. (1) Film peeling For each of Experimental Example 1 and Experimental Example 2, 100 electrophotographic photosensitive members were produced, and the number of film peeling was evaluated based on Comparative Experimental Example 1 as follows.

◎ Very good than (h) of Experimental example 1 ○ Better than (h) of Experimental example △ Equivalent to (h) of Experimental example 1 (2) Electrophotographic characteristics Device (Canon NP
6030 was modified for the experiment) and electrophotographic characteristics were evaluated. Non-uniform charging: A high voltage of +6 KV is applied to the charging device to perform corona charging, and the surface potential of the dark portion of the electrophotographic photosensitive member is measured at the developing device position by a surface potential meter. Then, five points are measured in the axial direction of the electrophotographic photosensitive member, and the potential unevenness at this time is evaluated. Uneven sensitivity The electrophotographic photoreceptor is charged to a constant dark surface potential.
Immediately thereafter, a halogen lamp light excluding light in the wavelength range of 550 nm or less is irradiated by using a filter, and the light amount is adjusted so that the bright 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. Then, the sensitivity is measured at five points in the axial direction of the electrophotographic photoreceptor, and the sensitivity unevenness at this time is evaluated.

For each of the charging unevenness and the sensitivity unevenness,
It was divided into the following ranks.

◎ Very good ○ Good △ Practically no problem × Practically problematic Halftone chart with image roughness (Part number: FY9-9042-
No. 020) was used to form an image, and the obtained halftone image was observed in detail, and compared with a limit sample to be evaluated according to the following ranks.

◎ No rustiness was observed at all, it was very good. ○ Some rustiness was slightly observed, but it was good. △ There was a lot of rashness, but there was a lot of conventional level × rashiness, and there was a problem in practical use. Is shown in Table 3, and the evaluation results of Experimental Example 2 are shown in Table 4.

[0038]

[Table 3]

[0039]

[Table 4] From Table 3, it is found that setting P / (S2 / S1) to 5 W or more and 70 W or less has an effect on film peeling, and from Table 3, P / (f · S2 / S1) is 5 × 10 ⁻³ W / Sccm ~ 7
It was found that by setting the density to × 10 ^-1 W / sccm, uneven charging, uneven sensitivity, and image roughness are effective. Then, from the results of Experimental Example 1 and Experimental Example 2, that is, Table 3 and Table 4, P / (S2 / S1) was set to 5 W or more and 70 W or less, and P / (f · S2 / S1) was set to 5 × 10 ^−3. W / sccm
It was found that the effects of the present invention can be obtained by setting the above to 7 × 10 ^-1 W / sccm or less.

[0040]

【Example】

(Example 1) In the deposited film forming apparatus of FIG.
Using a high frequency power supply 109 of several 13.56 MHz,
Minium diameter 45mm, 40mm, 30mm and
Forming an a-Si: H film on a 25 mm cylindrical substrate 102
Then, a photoconductor for electrophotography was produced. In this experimental example, discharge
Of the aluminum-made cylindrical substrate 102 facing the surface.
Surface area (S1), cylindrical cathode made of aluminum
Surface area of electrode 101 (S2), high frequency power supply 109
Regarding the power (P) applied to the sword electrode 101, P /
Shown in Table 2 so that (S2 / S1) = 30W
An electrophotographic photosensitive member was produced according to the above conditions. SiH4
Ratio of P / (S2 / S1) to gas flow rate (f): P /
(F · S2 / S1) is lower blocking layer, photoconductive layer, surface protection
1.5 × 10 each in layers^-1W / sccm, 7.5x
10^-2W / sccm, 2.7 × 10 ^-1W / sccm
ing.

The electrophotographic photoconductors produced were evaluated for film peeling, charging unevenness, sensitivity unevenness, and image roughness in the same manner as in Experimental Example 1. All electrophotographic photoconductors of Experimental Example 1 ( Good results were obtained as in b), (c), (d), (e) and (f). Furthermore, when the obtained photoconductor was installed in a Canon copying machine NP-6030 which was modified for an experiment and an image was produced, there was no unevenness in the halftone image.
A uniform image was obtained. Further, when a character original was copied, a clear image with high black density was obtained. Also, in copying a photo original, an image faithful to the original could be obtained. (Embodiment 2) In the deposited film forming apparatus of FIG. 2, a high frequency power source 209 having an oscillation frequency of 13.56 MHz was used to a-Si: H on a cylindrical substrate 102 made of aluminum and having a diameter of 45 mm, 40 mm, 30 mm and 25 mm. A film was formed and an electrophotographic photoreceptor was produced. In this embodiment, the surface area (S1) of the aluminum-made cylindrical substrate 102 facing the discharge surface, the surface area of the aluminum-made cylindrical cathode electrode 101 (S2), the high frequency power source 209 to the cathode electrode 201. Applied power (P) 10
The surface area (S2) of 1 and the electric power (P) applied from the high frequency power source 209 to the cathode electrode 201 are P / (S2 /
An electrophotographic photosensitive member was produced according to the conditions shown in Table 5 so that S1) = 65 W. Ratio of P / (S2 / S1) to SiH4 gas flow rate (f): P / (f · S
2 / S1) is a lower blocking layer, a photoconductive layer, and a surface protective layer, which are 4.3 × 10 ⁻¹ W / sccm and 3.3 × 10 ⁻¹ W, respectively.
/ Sccm, 3.3 × 10 ⁻¹ W / sccm → 6.5 × 1
It is 0 ^-1 W / sccm.

[0042]

[Table 5] Manufacturing conditions of electrophotographic photoreceptor Lower blocking layer ... SiH4 150 sccm SiF4 2 sccm H2 500 sccm B2H6 1500 ppm (relative to SiH4) NO 10 sccm CH4 5 sccm Internal pressure 40 Pa film thickness 2 μm Photoconductive layer ... SiH4 200 sccm SiF4 1 sccm H2 sccm B2H6 2ppm (for SiH4) NO 1sccm CH4 1sccm Internal pressure 53Pa Film thickness 30μm Surface protection layer ... SiH4 200sccm → 100sccm → 100sccm SiF4 5sccm B2H6 10ppm (for SiH4) NO 3sccm CH4 50sccm → 600sccm → 600sccm 0.5 μm The produced electrophotographic photosensitive member was subjected to film peeling, charging unevenness, When the unevenness and the roughness of the image were evaluated, good results were obtained for all the electrophotographic photoconductors as in (b), (c), (d), (e) and (f) of Experimental Example 1. Was obtained. Further, the obtained photoconductor was placed in a Canon copying machine NP-6030 which was modified for experiments and an image was produced. As a result, a uniform image was obtained without unevenness in the halftone image. Further, when a character original was copied, a clear image with high black density was obtained. Also, when copying a photo original, it was possible to obtain a clear image that was faithful to the original. (Embodiment 3) In the deposited film forming apparatus shown in FIG. 2, a high-frequency power source 209 having an oscillation frequency of 13.56 MHz was used to a-Si: H on a cylindrical substrate 202 made of aluminum and having a diameter of 45 mm, 40 mm, 30 mm and 25 mm. A film was formed and an electrophotographic photoreceptor was produced. In the present embodiment, the surface area (S1) of the aluminum-made cylindrical substrate 202 facing the discharge surface, the surface area of the aluminum-made cylindrical cathode electrode 201 (S2), and the high-frequency power source 209 to the cathode electrode 201. Applied power (P) P /
An electrophotographic photosensitive member was produced according to the conditions shown in Table 6 so that (S2 / S1) = 15 W. SiH4
Ratio of P / (S2 / S1) to gas flow rate (f): P /
(F · S2 / S1) is a lower blocking layer, a photoconductive layer, and a surface protective layer, which are 1 × 10 ⁻¹ W / sccm and 7.5 × 10, respectively.
^-2 W / sccm, 7.5 × 10 ^-2 W / sccm → 1.5
It is × 10 ^-1 W / sccm.

[0043]

[Table 6] Manufacturing Conditions of Electrophotographic Photoreceptor Lower blocking layer: SiH4 150 sccm SiF4 5 sccm H2 500 sccm B2H6 1500 ppm (relative to SiH4) NO 10 sccm CH4 5 sccm Internal pressure 40 Pa film thickness 2 μm photoconductive layer ... SiH4 200 sccm SiF4 3 sccm Hsc B2H6 3 ppm (relative to SiH4) Internal pressure 15 Pa Film thickness 30 μm Surface protective layer ... SiH4 200 sccm → 100 sccm → 100 sccm SiF4 10 sccm CH4 0 sccm → 500 sccm → 500 sccm Internal pressure 30 Pa Film thickness 0.5 μm Experimental example 1 Film peeling, charging unevenness, sensitivity unevenness, and image roughness were evaluated in the same manner as in (1) above. , (C), (d), (e), and (f), good results were obtained. Further, the obtained photoconductor was placed in a Canon copying machine NP-6030 which was modified for experiments and an image was produced. As a result, a uniform image was obtained without unevenness in the halftone image. Further, when a character original was copied, a clear image with high black density was obtained. In addition, a faithful and clear image could be obtained even when copying a photo original. (Embodiment 4) In the deposited film forming apparatus shown in FIG. 1, a high-frequency power source 109 having an oscillation frequency of 13.56 MHz was used to a-Si: H on a cylindrical substrate 102 made of aluminum and having a diameter of 45 mm, 40 mm, 30 mm and 25 mm. A film was formed and an electrophotographic photoreceptor was produced. In the present experimental example, the surface area (S1) of the aluminum-made cylindrical substrate 102 facing the discharge surface, the surface area of the aluminum-made cylindrical cathode electrode 101 (S2), the high frequency power supply 109 to the cathode electrode 101. Applied power (P) P /
An electrophotographic photosensitive member was produced according to the conditions shown in Table 7 so that (S2 / S1) = 20 W. SiH4
Ratio of P / (S2 / S1) to gas flow rate (f): P /
(F · S2 / S1) is a lower blocking layer, a photoconductive layer, and a surface protective layer, respectively, 6.7 × 10 ^-2 W / sccm, 2 × 10
⁻¹ W / sccm and 5 × 10 ⁻¹ W / sccm.

[0044]

[Table 7] Manufacturing conditions for electrophotographic photoreceptors   Lower blocking layer ... SiH4 300 sccm               H2 500sccm               B2H6 3000ppm (relative to SiH4)               NO 5 sccm               Internal pressure 27Pa               Film thickness 3μm   Photoconductive layer: SiH4 100 sccm               H2 600sccm               B2H6 5ppm (relative to SiH4)               NO 1 sccm               Internal pressure 20Pa               Film thickness 25 μm   Surface protection layer: SiH4 40 sccm               NH3 400sccm               Internal pressure 15Pa               Film thickness 0.3 μm The produced electrophotographic photoreceptor was peeled off in the same manner as in Experimental Example 1.
Evaluation of uneven charging, uneven sensitivity, and image roughness
As a result, all of the electrophotographic photoconductors of Experimental Example 1
Good as in (b), (c), (d), (e) and (f)
The results were obtained. Furthermore, the obtained photoconductor was modified for experiments.
Installed on Canon Copier NP-6030 and output images
However, the halftone image has no unevenness and a uniform image.
The image was obtained. When copying a text original, the black density
And a clear image was obtained. Also for copying photo manuscripts
Even though it was, I was able to obtain a clear image that was true to the original. (Example 5) In the deposited film forming apparatus of FIG.
Using a high frequency power source 209 of several 13.56 MHz,
Minium diameter 45mm, 40mm, 30mm and
Form a-Si: H film on 25 mm cylindrical substrate 202
Then, a photoconductor for electrophotography was produced. In this example, the discharge
Of the aluminum-made cylindrical substrate 202 facing the surface.
Surface area (S1), cylindrical cathode made of aluminum
Surface area of electrode 201 (S2), high frequency power source 209
Regarding the power (P) applied to the sword electrode 201, P /
Shown in Table 8 so that (S2 / S1) = 40W.
An electrophotographic photosensitive member was produced according to the above conditions. SiH4
Ratio of P / (S2 / S1) to gas flow rate (f): P /
(F · S2 / S1) is a photoconductive layer (first region), light
2.7 × each in the electric layer (second region) and the surface protective layer
10^-1W / sccm, 2.7 × 10 ^-1W / sccm, 4
× 10^-1W / sccm → 5.7 × 10^-1W / sccm →
6.7 x 10^-1It is W / sccm.

[0045]

Table 8 Manufacturing conditions of electrophotographic photoreceptor Lower blocking layer (first region) ... SiH4 150 sccm SiF4 5 sccm H2 500 sccm B2H6 10 ppm → 2 ppm (relative to SiH4) NO 1 sccm CH4 100 sccm → 0 sccm Internal pressure 30 Pa Film thickness 25 μm Light Conductive layer (second region) ... SiH4 150 sccm SiF4 5 sccm H2 500 sccm B2H6 2 ppm (relative to SiH4) Internal pressure 30 Pa Film thickness 3 μm Surface protection layer ... SiH4 100 sccm → 70 sccm → 60 sccm SiF4 1 sccm CH4 0 sccm → 50 sccm → 500 sccm The electrophotographic photosensitive member having a thickness of 0.5 μm was evaluated for film peeling, charging unevenness, sensitivity unevenness, and image roughness in the same manner as in Experimental Example 1. , None of the electrophotographic photoreceptor Experimental Example 1
Good results were obtained as in (b), (c), (d), (e), and (f).

Further, the obtained photoconductor was installed in a Canon copying machine NP-6030 which was modified for an experiment and an image was produced. As a result, a uniform image was obtained without unevenness in the halftone image. Further, when a character original was copied, a clear image with high black density was obtained. Also, when copying a photo original, it was possible to obtain a clear image that was faithful to the original.

[0047]

According to the deposited film forming method of the present invention, it is possible to provide a deposited film forming method capable of reducing film peeling when an electrophotographic photoreceptor having a diameter smaller than that of a conventional one is manufactured. it can.

Further, according to the deposited film forming method of the present invention, it is possible to manufacture a good electrophotographic photosensitive member which is free from uneven density, uneven sensitivity, and image roughness.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a deposited film forming apparatus used for forming a cylindrical substrate by using the deposited film forming method of the present invention.

FIG. 2 is a schematic view showing another example of the deposited film forming apparatus of the present invention.

[Explanation of symbols]

100, 200 deposition chamber 101, 201 cathode electrode 102, 202 cylindrical substrate 103, 203 auxiliary substrate 104, 204 heater for heating substrate 105, 205 rotation axis 106, 206 Raw material gas inlet 107, 207 Drive motor 108, 208 Matching device 109, 209 High frequency power supply 110, 210 exhaust port

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Furushima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-3-64466 (JP, A) JP-A-7 -233477 (JP, A) JP-A-6-252058 (JP, A) JP-A-5-291149 (JP, A) Actual flat 7-10934 (JP, U) Actual flat 6-50061 (JP, U) ) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01L 21/205 C23C 16/50 G03G 5/082

Claims (6)

(57) [Claims] 1. A diameter in which a substrate heating heater is fixed in a vacuum-tight deposition chamber equipped with an evacuation unit and a source gas supply unit, and an auxiliary substrate also serving as a discharge electrode is attached so as to enclose the substrate heating heater. A cylindrical substrate having a diameter of 45 mm or less is rotatably installed, and high-frequency power is applied between the cylindrical substrate and a cathode electrode which is provided coaxially and which is provided on the same axis to cause glow discharge to generate a glow discharge. In the method of forming a coaxial type deposited film by a plasma CVD method for forming a deposited film containing silicon on a cylindrical substrate, the surface area of the cylindrical substrate facing the glow discharge surface is Sl, the surface area of the cathode electrode is S2, and the surface area of the cathode electrode is S2. When the power applied to the cathode electrode is P and the flow rate of the SiH4 gas introduced into the deposition chamber is f, the following A and B equations 5W ≦ P / (S2 / S1) ≦ 70W ......... (A 5 × l0 ^over 3 W / sccm ≦ P / ( f · S2 / Sl) ≦ 7 × l0 -1 W / sccm ......... deposited film forming method characterized by satisfying (B). 2. The method for forming a deposited film according to claim 1, wherein a light receiving member including at least two layers of a photoconductive layer and a surface protective layer is formed on the cylindrical substrate. 3. The method for forming a deposited film according to claim 1, wherein a light receiving member including at least three layers of a lower blocking layer, a photoconductive layer and a surface protective layer is formed on the cylindrical substrate. 4. A diameter in which a substrate heating heater is fixed in a vacuum-tight deposition chamber equipped with an evacuation unit and a source gas supply unit, and an auxiliary substrate also serving as a discharge electrode is attached so as to enclose the substrate heating heater. A cylindrical substrate having a diameter of 45 mm or less is rotatably installed, and high-frequency power is applied between the cylindrical substrate and a cathode electrode that is provided on the same axis as the outer surface of the cylindrical substrate. In a coaxial type deposited film forming apparatus by a plasma CVD method for forming a deposited film containing silicon on a substrate, the surface area (S2) of the cathode electrode relative to the surface area (S1) of the cylindrical substrate facing the glow discharge surface is The ratio and the electric power (P) applied to the cathode electrode are set so as to satisfy the following expression A, and 5 W ≦ P / (S2 / S1) ≦ 70 W ... (A) and lead to the deposition chamber. SiH4 gas flow rate (f), so as to satisfy the following equation B ^{5 × l0 -3 W / sccm ≦} P / (f · S2 / Sl) ≦ 7 × l0 -1 W / sccm ......... to (B) A deposited film forming apparatus characterized by being set. 5. The deposited film forming apparatus according to claim 4, wherein a light receiving member having at least two layers of a photoconductive layer and a surface protective layer is formed on the cylindrical substrate. 6. The deposited film forming apparatus according to claim 4, wherein a light receiving member composed of at least three layers of a lower blocking layer, a photoconductive layer and a surface protective layer is formed on the cylindrical substrate.