JP2002038273A - Apparatus and method for plasma treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a deposition film with superior uniformity of the film characteristics and restricted occurrence of a picture failure. SOLUTION: This apparatus comprises a base body cap 107 having a flange part 118 with an external diameter wider than that of a cylindrical base body 105, which supports the cylindrical base body 105 for forming a deposition film, and a dashboard 113 arranged at a distance d from the surface of a lower part 119 of the base body cap without touching, in a reaction vessel. The dashboard 113 is arranged at the lower part 119 of the base body cap, so as not to influence the deposition film deposited on the surface of the cylindrical base body 105, and so that film pieces which are exfoliated from the main body of the base body cap 107 and the flange part 118, can not scatter toward the cylindrical base body 105. The distance d is set at intervals which do not obstruct a formation of a sheath on the surface of the base body cap 107 and which are hard for the film pieces to pass. The dashboard 113 divides a glow discharge generating in the reaction vessel 101 into two of a first discharge region 116 and second discharge region 117.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma processing apparatus for forming a functional deposited film (for example, an amorphous semiconductor used for a semiconductor device, an electrophotographic photosensitive member, a photovoltaic device, etc.) on a substrate and the like. The present invention relates to a plasma processing method.

[0002] The term "plasma processing" used in the description of the present specification means plasma processing such as etching and ashing in addition to processing of forming a deposited film. That is, the plasma processing apparatus is an etching apparatus,
And an ashing device.

[0003]

2. Description of the Related Art In digital copiers and color copiers, which have been remarkably popular in recent years, not only text documents but also photographs,
Since pictures, design pictures, etc. are frequently copied, the demands for reducing the density unevenness of the copied images and reducing image defects are extremely high, and it is urgently necessary to realize an electrophotographic photoreceptor capable of coping with this. Has become.

[0004] In addition, the demand for electrophotographic photoconductors having a smaller diameter than before has been increasing due to the demand for smaller electrophotographic photoconductors as copiers and printers, and development of manufacturing apparatuses capable of achieving cost reduction. Is also desired.

In such a situation, a vacuum deposition method is used as a plasma processing method for an element member used for a semiconductor device, an electrophotographic photosensitive member, an image input line sensor, an imaging device, a photovoltaic device, and other various electronic elements. , Sputtering, ion plating, thermal CVD, optical CVD, plasma CVD
Many methods, such as the method, are known, and a device for this is put to practical use. Among them, the plasma CVD method, that is, a method of decomposing a raw material gas by direct current or high frequency or microwave glow discharge to form a thin film deposition film on a substrate is most preferably hydrogenated amorphous silicon (hereinafter referred to as “a- At present, practical use is extremely advanced, such as formation of a deposited film (denoted as "Si: H"), and various apparatuses for this purpose have been proposed.

FIG. 7 shows an example of a plasma CVD apparatus generally used for forming such an a-Si: H film. The plasma CVD apparatus shown in FIG. 7 is an a-Si: H film plasma processing apparatus for a cylindrical electrophotographic photosensitive member by VHF plasma CVD using VHF band high frequency as a high frequency power supply. FIG. 7B is a longitudinal sectional view, and FIG.

In a reaction vessel 501 of the a-Si: H film plasma processing apparatus, which can be decompressed, a substrate cap 507 for supporting a cylindrical substrate 505 on which a deposited film is to be formed and a cylindrical substrate 505 are placed from the inside. A substrate holder 506 having a built-in heater 509 for heating to a predetermined temperature;
01 is provided, and a high-frequency power supply 503 is connected to the matching box 50.
4 is connected to the cathode electrode 502. Further, a base body auxiliary member is constituted by the base body cap 507 and the base body holder 506 respectively joined to the cylindrical base body 505. Further, the reaction vessel 501 is connected via an exhaust port 512 to a vacuum exhaust unit (not shown) such as a vacuum pump for reducing the pressure inside the reaction vessel 501.

[0008] Further, as shown in FIG.
The cylindrical substrate 505 is arranged at the center of the reaction vessel 501, and four raw material gas supply pipes 508, 4
Two exhaust ports 512 are arranged. In addition, the reaction vessel 5
A cathode electrode 50 electrically opposed to the inside of the reaction vessel 501 by an insulating material as a counter electrode of the cylindrical base 505 on the circumference between the inner electrode 05 and the earth shield 510.
4 are arranged.

[0009] a-S using such a conventional film forming apparatus
The formation of the i: H film can be performed according to the following procedure.

First, the inside of the reaction vessel 501 is evacuated to a high vacuum by vacuum evacuation means connected to the other end of the exhaust port 512, and then silane gas is supplied through a raw material gas supply pipe 508.
Source gases such as disilane gas, diborane gas, methane gas, and ethane gas are introduced, and the inside of the reaction vessel 501 is maintained at a predetermined pressure.

Next, the high-frequency power supply 503 is set to a desired power, and the matching box 504 and the cathode electrode 50 are set.
2, VHF electric power is introduced into the reaction vessel 501,
Plasma is generated between the cathode electrode 502 and the cylindrical substrate 505 to decompose the source gas.

An a-Si: H film is deposited on the cylindrical substrate 505 heated to a predetermined temperature of, for example, 200 to 400 ° C. by the heater 509.

[0013]

The above-described conventional plasma processing apparatus and plasma processing method provide a good a
Although an -Si-based electrophotographic photoreceptor is formed, in consideration of actual production, further contrivance is required, and the following problems may occur.

When a glow discharge is generated by the high-frequency power introduced into the reaction vessel to form a deposited film on the substrate, the high-frequency power propagates through the space in the reaction vessel and is transmitted to the substrate to generate a high-frequency electric field. Becomes The high-frequency electric field generated on the base propagates on the base and is reflected at an end of the base to generate a reflected wave. By combining the reflected wave and the high-frequency electric field (incident wave) before reaching the end of the base, a standing wave of the high-frequency electric field is generated on the base. When a standing wave of a high-frequency electric field is generated on the substrate, the electric field is weakened at the nodes of the standing wave and is increased at the antinodes. The strength of the electric field affects the plasma characteristics in the vicinity of the substrate, and in some cases, causes non-uniformity in the characteristics of the deposited film. In addition, the effect of the high-frequency electric field standing wave on the deposited film characteristics is small at a position distant from the reflection end because the reflected wave is attenuated in the reaction vessel due to the attenuation of the reflected wave. The effect of the standing wave is likely to appear remarkably in the near node portion.

As one of the methods for reducing the influence of the standing wave generated on the base, a method of adjusting the length of the base auxiliary member in the generatrix direction has been proposed.
The reflection end can be moved away from the base, and the node can be moved by moving the node of the standing wave of the high-frequency electric field toward the base auxiliary member. However, when the length of the base assisting member is increased, the film peeled off from the base assisting member scatters on the base, resulting in abnormal growth of the deposited film, which may cause image defects.

Accordingly, the present invention provides a plasma which is excellent in uniformity of the characteristics of a deposited film to be deposited, and which can form a deposited film in which occurrence of image defects is suppressed with good reproducibility, and which can be mass-produced at low cost. It is an object to provide a processing apparatus and a plasma processing method.

[0017]

In order to achieve the above object, a plasma processing apparatus according to the present invention has at least one substrate auxiliary member to which at least one substrate is joined in a decompressible reaction vessel, In a plasma processing apparatus for forming a deposited film on the substrate by introducing a source gas serving as a source of the deposited film into the reaction vessel and generating a glow discharge by high-frequency power, The bonding portion with each of the substrates, at a position not facing the surface on which the deposited film of each of the substrates is formed, and so as not to cut the sheath formed on each of the substrate auxiliary members and on each of the substrates, A first contact area, which is provided at an interval with respect to each base auxiliary member and contacts a discharge region of the glow discharge with the base.
And a second discharge region which is in contact with a part of the base auxiliary member.

In the plasma processing apparatus of the present invention configured as described above, the partition plate is spaced apart from the base assisting member, and the deposited film of each base at the joint between the base assisting member and the base is formed. It is provided at a position that does not face the surface to be processed.
Therefore, the partition plate does not cut the sheath formed on the base assisting member and the base, that is, since the sheath is continuously formed on the base assisting member and the base, the node of the standing wave is not cut. Can be moved to the base auxiliary member side. Further, since the partition plate is provided at a position that does not face the surface of the substrate on which the deposited film is formed, it hardly affects the formation of the deposited film on the surface of the cylindrical substrate. Further, the partition plate divides the discharge region of the glow discharge into at least two of a first discharge region in contact with the base and a second discharge region in contact with a part of the base auxiliary member. A state in which a deposited film is not easily formed on the base auxiliary member can be set.

Further, the plasma processing apparatus of the present invention may have a source gas supply means for supplying a source gas, or each substrate may have a cylindrical shape.

Each of the base assisting members may have a base holder joined to the lower end surface of the base and holding the base from the inside of the base. It may have a base cap bonded to the upper end surface of each base.

Further, the distance between the partition plate and each base auxiliary member may be in the range of 3 mm to 40 mm, and the material of the partition plate may be at least one of alumina, titanium dioxide, aluminum nitride, and boron nitride. It may be constituted by one.

Further, the plasma processing apparatus of the present invention has a first
A gas that is different from the source gas supplied to the discharge region and hardly affects the source gas and hardly contributes to the formation of a deposited film on each base auxiliary member. The gas supply means may have a supply means, and the gas supply means may supply at least one of a hydrogen gas, a nitrogen gas, a helium gas, and an argon gas.

A plasma processing method according to the present invention is a plasma processing method for forming a deposited film on at least one substrate using the plasma processing apparatus according to the present invention, wherein the source gas is supplied from the source gas supply means. A step of supplying a source gas to be supplied to the first discharge region; and forming a deposited film on each of the base auxiliary members, which is different from the source gas from the gas supply means and hardly affects the source gas. A gas supply step of supplying a gas that hardly contributes to the second discharge region, and a step of continuously forming the sheath on each of the base auxiliary members and each of the bases. .

According to the plasma processing method of the present invention as described above, the partition plate is spaced from the base auxiliary member,
In order to use the plasma processing apparatus of the present invention which is provided at a position where the deposited film of each substrate is not opposed to the bonding portion between the substrate auxiliary member and the substrate, the substrate auxiliary member and the substrate are The resulting sheath is not cut, and
The deposition film can be formed on the substrate in a state where the discharge region of the glow discharge is divided into at least two of a first discharge region in contact with the substrate and a second discharge region in contact with a part of the substrate auxiliary member. In addition, in the source gas supply step, the source gas is supplied to the first discharge region, and in the gas supply step, the source gas is hardly affected, and it is hard to contribute to the formation of a deposited film on each base auxiliary member. Since the gas is supplied to the second discharge region, the deposited film can be formed on the base in a state where an unnecessary deposited film is not easily formed on the base auxiliary member. Further, since the method includes a step of continuously forming a sheath on each of the base assisting members and on each of the bases, it is possible to form a deposited film on the base while moving a node of the standing wave toward the base assisting member. it can.

In the plasma processing method of the present invention, at least one of a hydrogen gas, a nitrogen gas, a helium gas, and an argon gas may be supplied in the gas supply step. Frequency 50-450M
It may include a step of applying high-frequency power in the range of Hz.

[0026]

Next, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view of an example of a plasma processing apparatus according to the present invention. FIG.
(B) is a side sectional view. FIG. 2 is an enlarged sectional view of the vicinity of the partition plate of the plasma processing apparatus shown in FIG.

In the reaction vessel 101 of the plasma processing apparatus of this embodiment, which can be decompressed, a substrate cap 107 joined to a cylindrical substrate 105 on which a deposited film is to be formed, and a cylindrical substrate 105 at a predetermined temperature from the inside. A base holder 106 having a built-in heater 106 for heating the base cap and a base cap 10 at a position facing the surface of the base cap lower part 119.
7, a source gas supply pipe 108 for introducing the source gas supplied from the source gas supply means 121 into the first discharge region 116, and a gas different from the source gas. Gas supply means 111 for introducing the gas into the second discharge region 117; and a high-frequency power source 103 is connected to the cathode electrode 102 via the matching box 104. The reaction vessel 101 is connected via an exhaust port 112 to a not-shown vacuum exhaust means such as a vacuum pump for reducing the pressure inside the reaction vessel 101.

Also, as shown in FIG.
The cylindrical substrate 105 is disposed at the center of the reaction vessel 101, and four source gas supply pipes 108, 4 are provided on the circumference of the reaction vessel 105 around the cylindrical substrate 105.
One exhaust port 112 is arranged. Also, the reaction vessel 1
The cathode electrode 10 is electrically insulated from the inside of the reaction vessel 101 by an insulating material as a counter electrode of the cylindrical substrate 105 on the circumference between the ground electrode 110 and the earth shield 110.
4 are arranged.

The base cap 107 is a cylindrical base 105.
The base holder 106 is joined to the lower end of the cylindrical base 105, and holds the cylindrical base 105 from the inside. The base holder 106 and the base cap 107 constitute a base auxiliary member.

As shown in FIG. 2, the shape of the base cap 107 may be a shape having a flange 118 whose outer diameter at the tip is larger than the outer diameter of the cylindrical base 105. Good. Such a shape can be adjusted by changing the outer diameter of the collar portion 118 for the length of the base cap 107 with respect to the standing wave. Thus, it is possible to adjust the length in the generatrix direction of the base auxiliary member for reducing the effect of the standing wave without changing the size of the reaction vessel 101 itself. Further, the base cap 10 having the flange 118
In the case of 7, since there is no need to extend the length of the reaction vessel 107 itself with the extension of the length of the base cap 107 in the generatrix direction of the base cap 107, there is no problem such as an increase in cost due to an increase in the size of the apparatus itself. . However, the base cap 107 is not limited to this, and may not have a flange like the base cap 107a shown in FIG. 3 depending on the configuration of the reaction vessel 107.

The material of the base cap 107 may be a metal such as aluminum, iron, chromium, magnesium, nickel or the like, or an alloy thereof, for example, stainless steel, in that the surface may be basically conductive. preferable.
Further, the base cap 107 needs to be in a conductive state with the cylindrical base 105. Therefore, the base cap 107
It is preferable that the joining portion 114 of the cylindrical base 105 and the joining portion 114 fit each other by soldering as shown in FIG.

The partition plate 113 is provided at a position separated by a distance d from the surface of the base cap lower portion 119 of the base cap 107.

That is, the position of the partition plate 113 in the height direction is determined so that the deposited film deposited on the surface of the cylindrical substrate 105 is not formed unevenly due to the presence of the partition plate 113. It is not provided at a position facing the surface of the cylindrical substrate 105 on which the deposited film is formed, and prevents the film pieces peeled from the substrate cap 107 main body and the brim portion 118 from scattering to the cylindrical substrate 105 side. Therefore, it is set in the lower portion 119 of the base cap. Further, by providing the partition plate 113 at this height position, the glow discharge generated in the reaction vessel 101 can be reduced.
A first discharge region 116 in contact with the substrate cap 107
And a second discharge region 117 that is in contact with a part of the second discharge region 117.

It should be noted that the partition plate 113 is formed of the cylindrical substrate 10.
If it is not provided at a position facing the surface on which the deposited film 5 is formed, it may be installed and fixed at the tips of the four source gas supply pipes 108.

The distance d from the surface of the base cap lower part 119 to the partition plate 113 does not obstruct the formation of the sheath on the surface of the base cap 107 because the distance d is too small.
In addition, when the distance d is too wide, the raw material gas is
As a result of diffusion through the gap between the base 3 and the base cap 107,
The distance must be such that a film piece peeled off from the substrate cap 107 to which the film has adhered can be prevented from adhering to the cylindrical substrate 105. Specifically, the distance d is preferably in the range of 3 to 40 mm, and more preferably in the range of 5 to 20 mm depending on the film forming conditions.

The material of the partition plate 113 is made of the reaction vessel 101.
The first discharge region 116 and the second discharge region
The discharge region 117 is preferable because it can be divided into two and a continuous sheath can be formed on the surfaces of the cylindrical base 105 and the base cap 107. Further, a material that does not easily cause the deposited film to peel off is preferable. Specifically, a ceramic member made of alumina, titanium dioxide, aluminum nitride, boron nitride, or the like is also preferable.

It is preferable that a gas supply unit 111 for supplying a gas different from the source gas to the discharge region in contact with the base cap 107 is provided in the reaction vessel 101. Second discharge region 117 in contact with base cap 107
In addition, by supplying a gas different from the source gas from the gas supply unit 111, it is possible to suppress the source gas from diffusing to the base cap 107 side through the gap between the base cap 107 and the partition plate 113. The use efficiency of the device is increased, and the cost can be reduced. Further, base cap 1
By preventing the film from being deposited on layer 07, film peeling from substrate cap 107 can be further reduced, and image defects can be suppressed.

The kind of gas supplied to the gas supply means 111 is such that hydrogen gas, nitrogen gas, helium, and the like are hardly affected by the raw material gas and hardly contribute to film adhesion to the base cap 107. It is preferable to use at least one selected from argon gas.

The gas supplied into the reaction vessel 101 is exhausted from an exhaust port 112 provided below the reaction vessel 101 by an exhaust device (not shown). Also, the base cap 10
The gas introduced into the second discharge region 117 in contact with 7 is
It is preferable that the air is exhausted by an exhaust device (not shown) from the exhaust port 115 provided in the upper part of the reaction vessel 101, but the present invention is not limited to this.

The supply of the high-frequency power to the cathode electrode 102 is guided to each cathode electrode 102 after the high-frequency power output from the high-frequency power supply 103 is divided into four parts via the matching box 104.

In this embodiment, the oscillation frequency of the high-frequency power supply output from the high-frequency power supply 103 is 50 MHz or more,
In the case of 450 MHz or less, a particularly remarkable effect can be obtained. If it is less than 50 MHz, high vacuum discharge becomes difficult, and if it is discharged at high pressure, particles such as polysilane are likely to be generated in the film formation space. These particles are particularly likely to be generated near the sheath, and the generation of particles near the partition plate 113 adjacent to the sheath deteriorates the properties of the entire film, and further, when the non-uniformity of the film properties significantly occurs. Therefore, it is difficult to obtain the effect of the present embodiment. On the other hand, above 450 MHz,
Since the raw material gas decomposition efficiency is high and the power absorption rate in the reaction vessel 101 is large, the high-frequency electric field generated on the cylindrical substrate 105 and the substrate cap 107 is
It is presumed that most of the reflected waves are attenuated before reaching the end portion of 07 and a reflected wave is generated there, and it is difficult to obtain the effect of enabling uniformity using the base cap 107. Therefore, an oscillation frequency of 50 to 450 MHz is optimal in the present embodiment.

Next, an example of a method for forming a deposited film on the cylindrical substrate 105 using the plasma processing apparatus of the present embodiment will be described.

First, the cylindrical substrate 105 degreased and washed in advance is placed on the substrate holder 109 in the reaction vessel 101, and the partition plate 113 is set and fixed to the tips of the four source gas supply pipes 108. Thereafter, the base cap 107 is fitted to the cylindrical base 105 so as to be in a conductive state.
After the installation of each member, the reaction vessel 1 is exhausted through the exhaust port 112 and / or the exhaust port 115 by an exhaust device such as a vacuum pump.
The inside of 01 is exhausted. Next, the temperature of the cylindrical base 105 is heated and controlled to a desired temperature by the heater 109.

When the temperature of the cylindrical substrate 105 reaches a desired temperature, a source gas is introduced into the reaction vessel 101 through a source gas supply pipe 108. Further, a gas different from the source gas is also introduced from the gas supply unit 111 at the same time.

Next, when the flow rate of the supply gas reaches the set flow rate, the exhaust valve (not shown) is adjusted while watching the vacuum gauge (not shown) to set the inside of the reaction vessel 101 to a desired internal pressure. After confirming that the internal pressure has stabilized, the high-frequency power source 103
Cathode electrode 1 via matching box 104
02 is supplied with a predetermined high frequency power. This high frequency power supply 1
The raw material gas introduced into the reaction vessel 101 is decomposed by the discharge energy of 03, and a deposited film is formed on the cylindrical substrate 105.

After the plasma treatment of a desired film thickness is performed,
The supply of the high-frequency power is stopped, and then the flow of gas into the reaction vessel 101 is stopped. In order to form a multi-layer deposited film on the cylindrical substrate 105 in order to obtain desired characteristics of the deposited film, the above operation may be repeated a plurality of times.

As described above, once the formation of one layer is completed, the discharge is completely stopped between the layers, and after the setting of the gas flow rate and the pressure of the next layer is changed, the discharge is restarted. It may occur to form the next layer, or the gas flow rate, pressure,
A plurality of layers may be formed continuously by gradually changing the high frequency power to the set value of the next layer.

The plasma processing apparatus according to the present embodiment
In addition to being able to perform plasma processing on the cylindrical substrate 105 having a cylindrical shape, the present invention can be applied to an apparatus capable of performing plasma processing on a polygonal or elliptical cylindrical substrate, or can be applied to a plasma processing apparatus for a flat substrate. You may.

As described above, according to the plasma processing apparatus of the present embodiment, the partition plate 113 is attached to the base cap lower part 1.
19 at a distance d, the cylindrical substrate 1
Since the sheath 05 and the sheath formed on the base cap 107 are formed continuously without being cut by the partition plate 113, the node of the standing wave can be moved onto the base cap 107.

Further, the partition 113 can divide the discharge region into a first discharge region 116 which contributes to the formation of a deposited film and a second discharge region 116 which hardly contributes to the formation of a deposited film. Formation of a deposited film on the base cap 107 can be reduced. Further, since the partition plate 113 is provided on the base cap 107 side and on the lower end side of the base cap 107, it does not affect the formation of a deposited film on the surface of the cylindrical base 105, and As much as possible, and it is possible to prevent the film fragments from scattering toward the cylindrical base 105 and adhering to the cylindrical base 105.

Thus, the plasma processing apparatus of this embodiment provided with the partition plate 113 can form a uniform deposited film on the cylindrical substrate 105.

Although the present invention has been described by taking the above embodiment as an example, the present invention is not limited to this.

[0054]

EXAMPLES Next, examples of the above-described embodiment will be described, but the present invention is not limited to these examples. (First Embodiment) FIGS. 4A and 4B are a longitudinal sectional view and a side sectional view schematically showing a plasma processing apparatus used in the present embodiment.

In this embodiment, an electrophotographic photosensitive member was formed on a mirror-finished cylindrical cylinder 205 of an Al cylinder using the plasma processing apparatus shown in FIG. The dimensions of the cylindrical substrate 205 were 358 mm in length and 80 mm in outer diameter, and the electrophotographic photosensitive member was formed under the conditions shown in Table 1 with the oscillation frequency of the high frequency power supply 203 set to 105 MHz. The configuration of the plasma processing apparatus used in this embodiment is shown in FIG.
The configuration is basically the same as that of the plasma processing apparatus shown in FIG. 1 except that the exhaust port 115 shown in FIG.

[0056]

[Table 1]

In this embodiment, the base cap 207 and the base holder 206 constituting the base auxiliary member are both made of aluminum. The shape of the base cap 207 should be such that the outer diameter of the tip is larger than the outer diameter of the cylindrical base 205 in order to minimize the size of the apparatus by shortening the length of the base cap 207 as much as possible. Part 218
Used was used.

In this embodiment, the reaction vessel 20
The glow discharge generated in the substrate 1 is divided into two parts, a first discharge region 216 in contact with the cylindrical base 205 and a second discharge region 217 in contact with a part of the base cap 207.
The partition plate 213 was installed and fixed on the four source gas supply pipes 208. The partition plate 213 is made of alumina,
The one having a thickness of 7 mm and a surface roughness of Rz = 20 μm was used. In addition, the distance d between the partition plate 213 and the base cap 207 was changed to seven types.

Further, in this embodiment, in addition to the four source gas supply pipes 208, gas supply means 2 different from the source gas is used.
11 and hydrogen gas was used as a supply gas.

The reaction vessel 201 used was made of a cylindrical alumina material. The cathode electrode 202 is
Four concentrically arranged at equal intervals around the cylindrical substrate 205 at a position outside the reaction vessel 201.

The procedure for forming the electrophotographic photosensitive member was roughly as follows.

First, the cylindrical substrate 205 is placed in the substrate holder 20.
9 and mounted thereon, and the partition plate 213 was installed and fixed to the tips of the four source gas supply pipes 208. Thereafter, the base cap 207 was fitted to the cylindrical base 205 so as to be in a conductive state. After the installation of each member was completed, the inside of the reaction vessel 201 was exhausted through the exhaust port 212 by an exhaust device (not shown).

After exhausting the inside of the reaction vessel 201, an argon gas is supplied into the reaction vessel 201 from the raw material gas supply pipe 208, and then the heater is maintained while maintaining the pressure inside the reaction vessel 201 at 70 Pa by a pressure adjusting valve (not shown). In step 209, the heating of the cylindrical substrate 205 was controlled to 250 ° C.

Then, the supply of the argon gas is stopped, the reaction vessel 205 is evacuated through the exhaust port 212 by the exhaust device, and then the source gas is supplied through the source gas supply pipe 208. Introduced hydrogen gas through another gas supply means 211.

After confirming that the total gas flow rate has reached the set flow rate and that the pressure in the reaction vessel 201 has stabilized, the power of the high-frequency power source 203 is set, and the matching box 204 is set.
Oscillation frequency of 105 MH.
z high frequency power was supplied. The source gas was excited and dissociated by high-frequency power radiated into the reaction vessel 201 from the cathode electrode 202, thereby forming a charge injection blocking layer on the cylindrical substrate 205. After the formation of the predetermined film thickness, the supply of the high-frequency power was stopped, and then the supply of the raw material gas and the hydrogen gas other than the raw material gas was stopped, thereby completing the formation of the charge injection blocking layer. By repeating the same operation a plurality of times, a photoconductive layer and a surface layer were sequentially formed. (First Comparative Example) In this comparative example, in the plasma processing apparatus shown in FIG. 4, the first plate was provided without providing a partition plate and gas supply means 211 for supplying a gas different from the source gas. An electrophotographic photosensitive member was formed under the conditions shown in Table 1 in the same manner as in the example.

Under the above conditions, the electrophotographic photosensitive members formed in the first embodiment and the first comparative example were installed in a Canon copier NP-6750 modified for this test to evaluate the characteristics. went.

The evaluation items "image density unevenness" and "image defect" were evaluated by the following specific evaluation methods. "Image density unevenness" First, after adjusting the charging device current so that the dark portion potential at the developing device position becomes a constant value, a predetermined white paper having a reflection density of 0.1 or less is used for the original, and the bright portion at the developing device position is used. The image exposure light amount was adjusted so that the potential became a predetermined value. Next, the Canon halftone chart (part number FY9-904)
2) was placed on a platen and evaluated by the difference between the maximum value and the minimum value of the reflection density in the entire area on the copy image obtained when copying was performed. Therefore, the smaller the value, the better. "Image defects" Canon full black chart (Part number: F
Y9-9073) was placed on a platen, and the number of white spots having a diameter of 0.2 mm or more in the same area of a copy image obtained when copying was counted, and evaluated by the number. Therefore, the smaller the numerical value, the better.

Table 2 shows the results of these evaluations.

[0069]

[Table 2]

In Table 2, a relative comparison was made with the value when formed in the first comparative example as 100. D in the table
Is the distance between the partition plate 213 and the base cap 207.

In the results shown in Table 2, the "image density unevenness" according to the present embodiment indicates that the first image was obtained when the distance d was 3 mm to 50 mm.
As good as the comparative example, good deposited film characteristics were observed. Further, the “image defect” according to the present embodiment is such that the distance d is 2 mm to
At 40 mm, it was clearly improved compared to the first comparative example.

When the distance d was 2 mm, the "image defect" according to the present embodiment was improved as compared with the first comparative example, but the "image density unevenness" according to the present embodiment was improved with respect to the partition plate 213 and the substrate. This is probably because the distance d from the cap 207 is smaller than the sheath length, so that the effect of moving the characteristic drop portion to the base cap 207 due to the propagation of the standing wave was small.

When the distance d was 50 mm, as to the “image density unevenness” according to the present example, the same deposited film characteristics as those of the first comparative example were recognized, but the “image defect” according to the present example was observed.
As for the raw material gas, the partition plate 218 and the base cap 2
It seems that as a result of the diffusion through the gap of 07, the effect of preventing the film pieces peeled from the substrate cap 207 to which the film has adhered from flying to the cylindrical substrate 205 was small.

As described above, in the plasma processing apparatus of this embodiment shown in FIG. 4, when the distance d is 3 mm to 40 mm, remarkable results are obtained in any of the items of “image density unevenness” and “image defect”. It was confirmed that it could be done.

Further, when the electrophotographic photosensitive member is formed by the plasma processing apparatus of the present embodiment, it is possible to suppress the source gas from diffusing into the discharge region in contact with the base cap 207, that is, the second discharge region 317. As a result, the gas use efficiency is reduced by 15 compared to the case formed in the first comparative example.
% And cost reduction became possible. (Second Embodiment) FIGS. 5A and 5B are a longitudinal sectional view and a side sectional view schematically showing a plasma processing apparatus used in this embodiment.

In this embodiment, an electrophotographic photosensitive member was formed in the same manner as in the first embodiment, using the plasma processing apparatus shown in FIG. In this embodiment, a base cap 307 having no flange is used instead of the base cap 307 having the flange used in the first embodiment.

In this embodiment, the gap between the partition plate 313 and the base cap 307 is set to d = 10 mm.

Further, in this embodiment, a gas supply means 311 for supplying a gas different from the source gas to the second discharge region 317 is provided, and a helium gas is used as a gas to be used. Apart from the exhaust port 312 for exhaust,
An exhaust port 315 was provided in the upper part of the reaction vessel 301, and the exhaust was also performed from the upper part of the reaction vessel 301.

An electrophotographic photosensitive member was formed under the conditions shown in Table 1 in the same manner as in the first embodiment except for the other constitution and the procedure for forming the photosensitive member. However, under the conditions shown in Table 1, helium gas instead of hydrogen gas was used under the same conditions as a gas species different from the source gas. (Second Comparative Example) In this comparative example, an electrophotographic photosensitive member was formed under the conditions shown in Table 1 in the same manner as in the second embodiment, using the plasma processing apparatus shown in FIG.

In this comparative example, the partition plate 31
No gas supply means 311 for supplying a gas different from 3 and the source gas is provided.

Under the above conditions, the second embodiment, the second
The electrophotographic photosensitive member formed in Comparative Example 1 was evaluated for “image density unevenness” and “image defect” by the same evaluation method as in the first example.

As for “image density unevenness”, the present embodiment and the second comparative example were found to have the same level of good deposited film characteristics.

Table 3 shows the results of evaluation of the item "image defect" according to the present embodiment.

[0084]

[Table 3] In Table 3, the value when formed in the second comparative example is 10
Relative comparison was performed with 0.

As is clear from Table 3, by using the plasma processing apparatus of this embodiment shown in FIG. 5, good results were obtained in the item of "image defect" as compared with the second comparative example. Was confirmed.

When the electrophotographic photosensitive member is formed by the plasma processing apparatus of this embodiment, it is possible to suppress the source gas from diffusing to the first discharge region 316 contacting the base cap 307, and as a result, The gas use efficiency was improved by 13% as compared with the case of the second comparative example, and the cost was reduced. (Third Embodiment) Next, FIGS. 6A and 6B
Next, a vertical sectional view and a side sectional view schematically showing the plasma processing apparatus used in this example are shown.

In this embodiment, using the plasma processing apparatus shown in FIG. 6, an electrophotographic photosensitive member is placed on a cylindrical base 405 of a mirror-finished Al cylinder, six concentrically arranged at equal intervals. Was formed.

The dimensions of the cylindrical base 405 and the oscillation frequency of the high-frequency power supply 403 are the same as those in the first embodiment. The dimensions of the cylindrical base 405 are 358 mm in length and 80 mm in outer diameter.
mm, and the oscillation frequency of the high-frequency power supply 403 is 105 M
Hz. Then, an electrophotographic photosensitive member was formed under the conditions shown in Table 4.

[0089]

[Table 4]

In the present embodiment, the gap between the partition plate 413 and the base cap 407 is d = 20 mm, and the base cap 407 has a flange 418 similar to that used in the first embodiment. One used.

In this embodiment, the reaction vessel 40
In the first discharge region 416 where the glow discharge generated in the substrate 1 is in contact with the cylindrical substrate 405, one source gas supply pipe 408 is provided at the center of the reaction vessel 401, and the substrate cap 40
A gas supply unit 411 for supplying a gas different from the source gas was provided in the second discharge region 417 in contact with a part of the gas supply source 7. Hydrogen gas was used as a different gas from the source gas.

Six cathode electrodes 402 were arranged at equal intervals on the same circumference at a position outside the reaction vessel 401.

The procedure for forming the electrophotographic photosensitive member was the same as that of the first embodiment under the conditions shown in Table 5. As a forming procedure in this embodiment, the partition plate 413 is installed
The partition plate 413 was sandwiched and fixed in the reaction vessel 401 divided into two.

[0094]

[Table 5] (Third Comparative Example) In this comparative example, the plasma processing apparatus shown in FIG. 6 was used, and the partition plate 413 and gas supply means 411 for supplying a material gas different from the source gas were used.
An electrophotographic photoreceptor was formed under the conditions shown in Table 4 in the same manner as in Example 3 except that No. was provided.

Under the above conditions, the electrophotographic photosensitive members formed in the present example and the third comparative example were evaluated by the same evaluation method as in the first and second examples for “image density unevenness” and “image defect”. Was evaluated.

Regarding the “image density unevenness”, the same level of good deposited film characteristics was observed between the present example and the third comparative example.

Table 5 shows the results of evaluation of the item "image defect". In Table 5, a relative comparison was made with the value when formed in the third comparative example as 100.

As is evident from Table 5, it was confirmed that the use of the plasma processing apparatus of this embodiment provided better results in the item of "image defect" as compared with the third comparative example. .

When an electrophotographic photosensitive member is formed by the plasma processing apparatus of this embodiment, the substrate cap 407
It is possible to suppress the source gas from diffusing toward the second discharge region 416 in contact with the substrate, and as a result, the gas use efficiency is improved by 23% as compared with the case where the source gas is formed in the third comparative example, and the cost can be reduced. became.

[0100]

As described above, according to the present invention, the position where the sheath is not cut and the position where the deposited film of each substrate is not faced at the joint between the substrate auxiliary member and the substrate. By providing the partition plate, it is possible to prevent the scattering of the film fragments from the base auxiliary member to the base side while moving the node of the standing wave to the base auxiliary member side. Further, since the partition plate divides the discharge region into at least two portions, it is possible to make it difficult for a deposited film to be formed in the second discharge region on the side of the base auxiliary member, thereby suppressing the generation of film fragments. be able to.

As described above, it is possible to form a deposited film having excellent uniformity and suppressed occurrence of image defects with good reproducibility, and mass production can be performed at low cost.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view and a side sectional view of an example of a plasma processing apparatus according to the present invention.

FIG. 2 is an enlarged cross-sectional view near a partition plate of the plasma processing apparatus shown in FIG.

FIG. 3 is an enlarged sectional view showing an example of a base cap having a different shape in the plasma processing apparatus according to the present invention.

FIG. 4 is a schematic longitudinal sectional view and a side sectional view of the plasma processing apparatus used in the first embodiment of the present invention.

FIG. 5 is a schematic longitudinal sectional view and a side sectional view of a plasma processing apparatus used in a second embodiment of the present invention.

FIG. 6 is a schematic longitudinal sectional view and a side sectional view of a plasma processing apparatus used in a third embodiment of the present invention.

FIG. 7 is a schematic longitudinal sectional view and a side sectional view of an example of a conventional plasma processing apparatus.

[Explanation of symbols]

101, 401 Reaction vessel 102, 402 Cathode electrode 103, 203 High frequency power supply 104, 204 Matching box 105, 205, 305, 405 Cylindrical substrate 106 Substrate holder 107, 107a, 207, 307, 407 Substrate cap 108, 408 Source gas supply Pipe 109, 209 Heater 110 Earth shield 111, 211, 311, 411 Gas supply means 112, 212, 312, 412, 415 Exhaust port 113, 213, 313, 413 Partition plate 114 Joint 115, 315 Exhaust port 116, 216 , 316, 416 First discharge area 117, 217, 317, 417 Second discharge area 118, 218, 418 Collar 119 Lower part of base cap 121 Source gas supply means

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Otsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Toshiyasu Shirasuna 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon F term in reference (reference) 2H068 DA00 EA24 4K030 AA16 AA18 BA30 BA31 CA14 EA01 FA01 GA01 KA12

Claims (12)

[Claims] 1. A method according to claim 1, wherein at least one of
Having at least one substrate auxiliary member to which two substrates are joined, and introducing a source gas as a source of the deposited film into the reaction vessel to generate a glow discharge by high-frequency power, thereby forming a glow discharge on the substrate. A plasma processing apparatus for forming a deposited film on a substrate, wherein a joining portion between each of the substrate assisting members and each of the substrates is located at a position not facing a surface on which the deposited film of each of the substrates is formed, and A first discharge region, which is provided at an interval with respect to each of the substrate assisting members, so that a discharge region of the glow discharge is in contact with the substrate so as not to cut a sheath formed on the substrate and on each of the substrates. A plasma processing apparatus, comprising: a partition plate that is divided into at least two of a second discharge region that is in contact with a part of a base auxiliary member. 2. The plasma processing apparatus according to claim 1, further comprising source gas supply means for supplying the source gas. 3. The apparatus according to claim 1, wherein each of the substrates has a cylindrical shape.
Or the plasma processing apparatus according to 2. 4. The substrate supporting member according to claim 1, wherein each of the substrate auxiliary members has a substrate holder joined to a lower end surface of each of the substrates and holding the respective substrates from inside the respective substrates. 3. The plasma processing apparatus according to 1. 5. The plasma processing apparatus according to claim 1, wherein each of the base auxiliary members has a base cap joined to an upper end surface of each of the bases. 6. The plasma processing apparatus according to claim 1, wherein the distance between the partition plate and each of the base auxiliary members is in a range of 3 mm to 40 mm. 7. The plasma processing apparatus according to claim 1, wherein a material of the partition plate is at least one of alumina, titanium dioxide, aluminum nitride, and boron nitride. . 8. A source gas, which is different from the source gas supplied to the first discharge region, hardly affects the source gas,
8. The plasma processing apparatus according to claim 1, further comprising a gas supply unit configured to supply a gas that hardly contributes to formation of a deposited film on each of the base auxiliary members to the second discharge region. 9. . 9. The gas supply means includes at least one of a hydrogen gas, a nitrogen gas, a helium gas, and an argon gas.
9. The plasma processing apparatus according to claim 8, wherein one is supplied. 10. A plasma processing method for forming a deposited film on at least one substrate using the plasma processing apparatus according to claim 1, wherein the source gas is supplied from the source gas supply unit to the first substrate. A step of supplying a source gas to be supplied to the first discharge region; and forming a deposited film on each of the base auxiliary members by hardly affecting the source gas, which is different from the source gas, from the gas supply unit. A plasma supplying step of supplying a gas that hardly contributes to the second discharge region; and a step of continuously forming the sheath on each of the base auxiliary members and each of the bases. Processing method. 11. The plasma processing method according to claim 10, wherein at least one of a hydrogen gas, a nitrogen gas, a helium gas, and an argon gas is supplied in the gas supply step. 12. An oscillation frequency of 50 to 50 in said reaction vessel.
12. The plasma processing method according to claim 10, further comprising a step of applying a high-frequency power in a range of 450 MHz.