JP2005298873A - Plasma treatment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plasma treatment device capable of enhancing uniformity of the power distribution in a reaction vessel, realizing uniform quality of a film to be deposited, and forming the deposit film of excellent quality with excellent productivity. <P>SOLUTION: The plasma treatment apparatus to perform plasma treatment to a base body installed in a reaction vessel has a power divider unit to divide the high frequency power to a plurality of high frequency power transmission units, a plurality of high frequency electrodes to be connected to each high frequency power transmission unit, and a power divider vessel which houses the power divider unit and the plurality of high frequency power transmission units and is made of conductive members. At least a part of the reaction vessel is made of conductive members, at least a part of the conductive members of the reaction vessel form a part of the power divider vessel. A shield member made of the conductive member is installed in the power divider vessel, and the shield member is installed between the power divider unit and the plurality of high frequency power transmission units, and a conductive part of the reaction vessel to form a part of the power divider vessel. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a plasma processing apparatus for performing plasma processing on a substrate installed in a reaction vessel.

  As one of the deposited film forming methods, there is a plasma CVD method using discharge energy. An amorphous thin film (for example, amorphous silicon compensated by hydrogen or / and halogen) formed by this method is an electrophotographic photoreceptor, Applications to semiconductor elements such as semiconductor devices and TFTs have been proposed, and some of them have been put into practical use. In particular, the plasma CVD method using high-frequency power in the 13.56 MHz RF band is widely used because the substrate material, deposited film material, etc. can be processed regardless of the conductor or insulator, and the handling is relatively easy. ing. In recent years, the plasma CVD method using high-frequency power in the VHF band has attracted attention, and development of various deposited film forming methods using this method has been actively promoted. This is because in the VHF-PCVD method, the film deposition rate is high and a high-quality deposited film can be obtained, so that it is expected that cost reduction and high quality of the product can be achieved at the same time (for example, Patent Document 1). In addition, in order to further increase the productivity in the VHF-PCVD method, development of a technique for simultaneously forming a deposited film on a plurality of substrates using a plurality of electrodes has been actively promoted. As a result, by realizing uniform power division into a plurality of electrodes, it has become possible to treat a plurality of substrates uniformly, and higher productivity has been realized (for example, Patent Document 2). reference).

  FIG. 3A is a schematic configuration diagram showing a typical example of a conventional electrophotographic photoreceptor manufacturing apparatus using the VHF-PCVD method. FIG. 3A is a schematic cross-sectional view of the manufacturing apparatus as viewed from the side, and FIG. 3B is a schematic cross-sectional view as viewed from directly above along the cutting line X-X ′ in FIG. 3A.

  An example of a method for producing an electrophotographic photoreceptor when the production apparatus shown in FIG. 3 is used is shown below.

  The high frequency power output from the high frequency power supply 113 is introduced into the power dividing container 115 made of a conductive member after passing through the matching circuit 114. Next, the high frequency power introduced into the power dividing container 115 is divided into a plurality of high frequency power transmission units 117 by the power dividing unit 116 installed in the power dividing container 115, and then via the high frequency electrode 109. It is introduced into the reaction vessel 101. The source gas is introduced into the reaction vessel 101 from the source gas introduction means 103 and decomposed by plasma, and a deposited film is formed on the substrate 102.

By using such a manufacturing apparatus, it is possible to obtain a high-quality deposited film even at a high deposition film forming speed by the VHF-PCVD method, and it becomes possible to uniformly treat a plurality of substrates simultaneously. Product cost and quality can be reduced.
Japanese Patent Laid-Open No. 06-287760 (page 17, FIG. 1) Japanese Patent Laid-Open No. 2001-316829 (page 17, FIG. 1)

  However, there is room for further improvement in improving the quality of the deposited film formed in the manufacturing apparatus described above. One of them is that the plasma distribution in the reaction vessel becomes non-uniform, and quality unevenness may occur in the deposited film formed on the substrate.

  In the apparatus shown in FIG. 3, the plasma distribution in the axial direction of the substrate 102 in the reaction vessel 101 is made as uniform as possible by installing the high-frequency electrode 109 and the substrate 102 substantially in parallel. Further, the upper lid 107 which is a part of the reaction vessel 101 is made of a conductive member, thereby preventing high frequency power from being directly introduced into the reaction vessel 101 from the power dividing unit 116 or the high frequency power transmission unit 117. The plasma distribution in the axial direction of the substrate 102 in the reaction vessel 101 is made as uniform as possible.

  However, when a deposited film is formed using high frequency power in the VHF band with such an apparatus, sufficient uniformity may not be obtained in the quality of the deposited film formed on the substrate.

  The reason is not clear, but I guess as follows. When using high frequency power in the VHF band, the high frequency power may propagate to the conductive portion of the reaction vessel. It may happen even if the conductive part is grounded. The conductive portion of the reaction vessel through which the high-frequency power is propagated in this way functions as if it were a high-frequency electrode, so that high-frequency power may be introduced into the reaction vessel from a portion other than the original high-frequency electrode. is there. As a result, the distribution of plasma in the reaction vessel becomes non-uniform, and quality unevenness may occur in the deposited film formed on the substrate.

  For example, in the manufacturing apparatus shown in FIG. 3, high-frequency power may propagate to the upper lid 107 and high-frequency power may be introduced into the reaction vessel 101 through the upper lid 107. As a result, the plasma in the upper part of the reaction vessel 101 becomes strong, and quality unevenness may occur in the substrate axial direction of the deposited film to be formed.

  In order to prevent the high-frequency power from propagating as much as possible to the conductive member other than the transmission unit with respect to such a problem, for example, a manufacturing apparatus as shown in FIG. 4 can be considered. In the manufacturing apparatus shown in FIG. 4, similarly to the apparatus shown in FIG. 3, a power dividing unit 116 is installed in a power dividing container 115 made of a conductive member, and a plurality of high-frequency power transmission units 117 are connected. The high frequency power is divided. 3 differs from FIG. 3 in that the high-frequency power transmission unit 117 is connected to the coaxial cable 419 installed outside the power dividing container 115 and then connected to the high-frequency electrode 109.

  As a result of investigations using the apparatus shown in FIG. 4, the present inventors have improved the uniformity of plasma in the axial direction of the substrate and greatly improved the quality unevenness of the deposited film formed on the substrate. I understood. However, when the apparatus shown in FIG. 4 is used, it has also been confirmed that there may be a problem that the quality of the deposited film between different substrates may be uneven. Although the cause is not clear at this stage, in the apparatus shown in FIG. 4, in order to individually shield the transmission parts after power branching, the impedance of each transmission part varies slightly, so the power is uniform. In some cases, it may not be easy to divide into two, and as a result, the plasma distribution in the horizontal direction of the reaction vessel may be uneven.

  As a result of intensive investigations on such problems, the present inventors have realized that the uniformity of the plasma distribution in the reaction vessel is improved by optimizing the shield configuration of the high-frequency power transmission unit. The present invention has been completed.

  That is, the plasma processing apparatus of the present invention is a plasma processing apparatus for performing plasma processing on a substrate installed in a reaction vessel. A matching circuit, and high-frequency power after passing through the matching circuit are transferred to a plurality of high-frequency power transmission units. A power dividing container formed of a conductive member, including a power dividing unit to be divided, a plurality of high frequency electrodes connected to each of the plurality of high frequency power transmitting units, the power dividing unit and the plurality of high frequency power transmitting units. The reaction vessel is formed of at least a part of a conductive member, and includes the power dividing unit and the plurality of high frequency power transmission units, and a conductive part of the reaction vessel forming a part of the power dividing vessel. A shield member formed of a conductive member is provided between them.

  The effects of the present invention will be described in detail below.

  FIG. 1 shows an example of a schematic view of an electrophotographic photoreceptor manufacturing apparatus used in the present invention. In the apparatus shown in FIG. 1, the forms of the power dividing unit 116 and the high-frequency power transmission unit 117 after power division are the same as those of the apparatus shown in FIG. A difference from the apparatus shown in FIG. 3 is a portion where a shield member 119 is newly installed in the power dividing container 115. The shield member 119 described above is installed so as to cover the entire upper lid 107 between the power dividing unit 116 and the high-frequency power transmission unit 117 and the upper lid 107 which is a conductive portion of the reaction vessel.

  As a result, the uneven plasma distribution in the axial direction of the substrate in the reaction vessel is eliminated, and the uneven quality of the deposited film formed on the substrate is greatly improved. Although the cause is not certain, by installing the shield member 119 between the power dividing unit 116 and the high frequency power transmission unit 117 and the upper cover 107, high frequency power is prevented from propagating to the upper cover 107, and the high frequency electrode 109 is prevented. It is presumed that the adverse effect of introducing high-frequency power into the reaction vessel 101 from other members was prevented.

  Further, when the apparatus shown in FIG. 1 was used, it was also confirmed that the quality unevenness between different substrates could be greatly reduced as compared with the case where the apparatus shown in FIG. 4 was used. . The reason for this is not clear, but it is speculated that the plurality of high-frequency power transmission units 117 after the high-frequency power division are not individually shielded to enable even power division with higher accuracy. .

  Further, the conductive portion of the reaction vessel in the present invention refers to a portion directly exposed to plasma in the conductive portion constituting the reaction vessel. For example, FIG. 2 is an enlarged view of the vicinity of the upper lid 107 in FIG. 1, but the conductive portion constituting the reaction vessel in FIG. 2 is the portion indicated by the hatched portion in the drawing.

  In the present invention, it is more preferable that at least a part of the reaction vessel is made of a dielectric member, and the high-frequency electrode is installed outside the reaction vessel. This is because it may be easy to limit the area of the conductive portion exposed to the plasma in the reaction vessel.

  In the present invention, when using a high-frequency power source capable of supplying high-frequency power in the VHF band having a frequency of 50 MHz or more and 250 MHz or less, the effect appears remarkably. The reason for this is not clear, but at a high frequency of 50 MHz or higher, high-frequency power tends to propagate to the conductive portion of the device. Therefore, it is presumed that the shielding effect for the conductive portion of the reaction vessel, which is achieved by the present invention, appears remarkably at a high frequency of 50 MHz or higher. Further, at a high frequency of 250 MHz or higher, since the attenuation of the high frequency power is significant when propagating through the transmission section, it is not easy to generate uniform plasma in the reaction vessel, and the effects of the present invention are sufficiently obtained. I guess I can't get it.

  In the present invention, when a plurality of high-frequency power sources capable of supplying high-frequency powers having different frequencies are used and a plurality of high-frequency powers having different frequencies are used in a superimposed manner, the effect is remarkable. The reason is not clear, but in the case of using high-frequency power of a plurality of frequencies, the degree of propagation to the conductive portion may vary depending on the frequency. Therefore, when high-frequency power is introduced into the reaction vessel through the conductive portion of the reaction vessel, plasma unevenness occurs for each frequency in the base axis direction, and it is difficult to obtain the effect of superimposing a plurality of frequencies. There is a case. Therefore, it is considered that the effect of the present invention appears remarkably in the case where high frequency power of a plurality of frequencies is used.

  In the present invention, more remarkable effects can be obtained when the substrate used is cylindrical.

  Although the details of the present invention have been described above, this will be organized and described below.

  (1) In a plasma processing apparatus for performing plasma processing on a substrate installed in a reaction vessel, a matching circuit, a power dividing unit that divides high-frequency power after passing through the matching circuit into a plurality of high-frequency power transmission units, A plurality of high-frequency electrodes connected to each of a plurality of high-frequency power transmission units, including the power dividing unit and the plurality of high-frequency power transmission units, and including a power dividing container formed of a conductive member, A part is formed of a conductive member, and is formed of a conductive member between the power dividing unit and the plurality of high-frequency power transmission units and a conductive part of the reaction vessel forming a part of the power dividing container. A plasma processing apparatus, wherein the shield member is installed.

  (2) The plasma processing apparatus according to (1), wherein at least a part of the reaction vessel is made of a dielectric member, and the high-frequency electrode is installed outside the reaction vessel.

  (3) The plasma processing apparatus according to any one of (1) and (2), further comprising a high frequency power source capable of supplying high frequency power having a frequency of the high frequency power of 50 MHz to 250 MHz.

  (4) The high-frequency power source includes a plurality of high-frequency power sources capable of supplying high-frequency power having different frequencies, and a power superimposing unit that superimposes a plurality of high-frequency powers having different frequencies includes the matching circuit and the power dividing unit. The plasma processing apparatus according to any one of (1) to (3), wherein the plasma processing apparatus is installed between the two.

  (5) Any one of (1) to (4) above, wherein the conductive portion of the reaction vessel forming a part of the power dividing vessel is not parallel to the deposited film formation surface of the substrate. The plasma processing apparatus according to 1.

  (6) The plasma processing apparatus according to any one of (1) to (5), wherein the base is cylindrical.

  (7) The plasma processing apparatus according to any one of (1) to (6), wherein the plasma processing apparatus is used for forming a deposited film of an electrophotographic photoreceptor.

  The plasma processing apparatus of the present invention is a plasma processing apparatus for performing plasma processing on a substrate installed in a reaction vessel, and divides a high-frequency power after passing through the matching circuit into a plurality of high-frequency power transmission units. Including a power dividing unit, a plurality of high frequency electrodes connected to each of the plurality of high frequency power transmission units, the power dividing unit and the plurality of high frequency power transmission units, and a power dividing container formed of a conductive member, The reaction vessel is at least partially formed of a conductive member, and is between the power dividing unit and the plurality of high-frequency power transmission units and the conductive part of the reaction vessel forming a part of the power dividing vessel. By installing a shield member formed of a conductive member, the uneven plasma distribution in the axial direction of the substrate in the reaction vessel is eliminated while maintaining the uniform division of power, and the substrate is shaped. Quality unevenness of the deposited film to be made can be significantly improved.

  Next, the present invention capable of obtaining the above effects will be described in detail with reference to the drawings.

  FIG. 1 is an example of a schematic view of an electrophotographic photoreceptor manufacturing apparatus using a plasma CVD method used in the present invention, and is a schematic sectional view of the manufacturing apparatus as viewed from the side. FIG. 2 is an enlarged view of the vicinity of the upper lid of FIG. 1, and a hatched portion in the drawing indicates a portion of the upper lid that is directly exposed to plasma.

  The electrophotographic photoreceptor manufacturing apparatus shown in FIGS. 1 and 2 includes a reaction vessel 101 in which a cylindrical substrate 102 on which a deposited film is formed is installed. The substrate 102 is supported in the reaction vessel 101 by a substrate lower support means 105 and a substrate cap 106. A substrate heater 108 for heating the substrate 102 is disposed along the longitudinal direction of the substrate 102 inside the substrate 102. The base 102 can be rotated by a rotation mechanism 104. A cylindrical portion constituting the side wall of the reaction vessel 101 is made of a dielectric member. In the reaction vessel 101, a raw material gas introduction unit 103 connected to a gas supply device (not shown) outside the reaction vessel 101, a pressure regulator, a mass flow controller, and the like via a raw material gas introduction pipe 110 is disposed. Furthermore, the reaction vessel 101 has a pressure measuring means 111 for monitoring the internal pressure, and also includes a throttle valve 112 for communicating the inside of the vessel with the outside of the vessel by opening a valve whose opening degree can be adjusted.

  An earth shield 118 is provided outside the side wall of the reaction vessel 101 so as to surround the reaction vessel 101. A plurality of high-frequency electrodes 109 are evenly arranged around the reaction vessel 101 between the side wall of the reaction vessel 101 and the earth shield 118.

  Each of the plurality of high-frequency electrodes 109 is connected to the high-frequency power transmission unit 117 divided by the power dividing unit 116, and the power division unit 116 is connected to the matching circuit 114 via the high-frequency power transmission unit 117. The power transmission unit 117 is connected to the high frequency power supply 109.

  The power dividing unit 116 and the plurality of high-frequency power transmission units 117 are included in the power dividing container 115, and at least a portion of the power dividing unit 116 and the plurality of high-frequency power transmission units 117 and the upper lid 107 that are converted to plasma (see FIG. A shield member 119 is installed between the two hatched portions.

  Next, an example of the deposited film forming method according to the present invention, which is performed using the apparatus shown in FIGS. 1 and 2, will be described in detail below.

After the base body 102 is installed in the reaction vessel 101 at least partially made of a dielectric member, the inside of the reaction vessel 101 is evacuated using an exhaust device (for example, a vacuum pump). After the reaction vessel 101 is sufficiently evacuated, the required heating gas supplied from a gas cylinder such as He, N ₂ , Ar and H _{2 in} a gas supply device (not shown) is not shown. The flow rate is adjusted to an appropriate flow rate via a pressure regulator, a mass flow controller, and the like, and fed into the reaction vessel 101 via the raw material gas introduction pipe 110 and the raw material gas introduction means 103. The pressure in the reaction vessel 101 after the introduction of the heating gas is monitored by the pressure measuring means 111 and controlled to a predetermined value by adjusting the opening of the throttle valve 112 or the like. When the predetermined substrate heating environment is prepared, the substrate 102 is indirectly heated to a predetermined temperature by the substrate heater 108.

After completion of the predetermined heating, the required deposition film forming gas is supplied from a gas cylinder such as SiH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , and PH _{3 in} a gas supply device (not shown). However, the flow rate is adjusted to an appropriate flow rate via a pressure regulator, a mass flow controller, and the like, and is fed into the reaction vessel 101 via the raw material gas introduction pipe 110 and the raw material gas introduction means 103. The pressure in the reaction vessel 101 after the deposition film forming gas is introduced is monitored by the pressure measuring means 111 and controlled to a predetermined value by adjusting the opening of the throttle valve 112 or the like. When a predetermined deposition film forming environment is prepared, the high frequency power output from the high frequency power supply 113 is introduced into the power dividing container 115 formed of the wall surface maintained at a predetermined potential through the matching circuit 114. Thereafter, the high-frequency power is divided into a plurality of high-frequency power transmission units 117 in the power dividing unit 116 in the power dividing container 115, and after being output to the outside of the power dividing container 115, at least a part thereof is made of a dielectric member. Introduced into the reaction vessel 101 through a plurality of high-frequency electrodes 109 installed between the reaction vessel 101 and the earth shield 118, plasma is generated. The deposited film forming gas is decomposed by the plasma to form a deposited film on the substrate 102.

  Hereinafter, the effect of the present invention will be specifically described with reference to examples.

[Example 1]
In the plasma processing apparatus shown in FIG. 1, on the substrate 102 which is a cylindrical aluminum cylinder having a diameter of 80 mm and a length of 358 mm installed in the reaction vessel 101 by the above-described method using the high-frequency power source 113 having an oscillation frequency of 105 MHz. In addition, an electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 1.

[Comparative Example 1]
In this example, instead of the plasma processing apparatus used in the first embodiment, the plasma processing apparatus shown in FIG. 3 is used, and a high frequency power source 113 with an oscillation frequency of 105 MHz is used. An electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer under the conditions shown in Table 1 on a substrate 102, which is a cylindrical aluminum cylinder having a diameter of 80 mm and a length of 358 mm, installed in 101. Created.

[Comparative Example 2]
In this example, instead of the plasma processing apparatus used in the first embodiment, the plasma processing apparatus shown in FIG. 4 is used, and a high frequency power supply 113 with an oscillation frequency of 105 MHz is used. An electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer under the conditions shown in Table 1 on a substrate 102, which is a cylindrical aluminum cylinder having a diameter of 80 mm and a length of 358 mm, installed in 101. Created.

[Evaluation of Example 1 and Comparative Examples 1 and 2]
The electrophotographic characteristics of each of the six electrophotographic photoreceptors produced in Example 1 and Comparative Examples 1 and 2 were evaluated by the method described below, and the electrophotographic photoreceptor produced in Example 1 and the comparative example. Comparison with the electrophotographic photoreceptor prepared in 1 and 2 was performed.

"Evaluation method for unevenness of electrophotographic characteristics"
Each of the electrophotographic photoconductors prepared was installed in a Canon iR-5000 photocopier modified for this test. Evaluation items were “Charging capacity unevenness in the bus direction”, “Unevenness in sensitivity bus direction”, “Image” Each item was evaluated by the following specific evaluation method.

Uneven charging busbar direction
The dark portion potential at the position of the developing device when a constant current is passed through the main charger of the copying machine is defined as “charging ability” (however, the average value of one round in the circumferential direction). “Chargeability” was measured over the entire area of the electrophotographic photosensitive member in the busbar direction, and the difference between the maximum value and the minimum value with respect to the average value was evaluated as unevenness in chargeability. Therefore, the smaller the value, the better. “Electricity in the charging ability bus line direction” of each of the six electrophotographic photoreceptors prepared in Example 1 and Comparative Examples 1 and 2 was measured, and an average value between the six was obtained for each of them, and compared with Comparative Example 1. The value of Comparative Example 1 was set as 100%, and was classified into the following ranks.

A: Improvement to less than 50% compared to Comparative Example 1 B: Improvement to 50% or more and less than 75% compared to Comparative Example 1 C: Improvement to 75% or more compared to Comparative Example 1 or less D: Deteriorated compared to Comparative Example 1

"Unevenness of sensitivity bus direction"
After adjusting the current value of the main charger so that the dark portion potential at the developing unit position becomes a predetermined value, image exposure is performed. Next, the amount of light from the image exposure light source is adjusted so that the surface potential (bright potential) at the position of the developing device becomes a predetermined value, and the exposure amount at that time is defined as “sensitivity” (however, the average value in one circumferential direction) And). “Sensitivity” was measured over the entire area of the electrophotographic photosensitive member in the busbar direction, and the difference between the maximum value and the minimum value with respect to the average value was evaluated as sensitivity unevenness. Therefore, the smaller the value, the better. The “sensitivity in the direction of the sensitivity bus line” of each of the six electrophotographic photoreceptors prepared in Example 1 and Comparative Examples 1 and 2 was measured, and the average value between the six was determined in each case, and compared with Comparative Example 1. The value of Comparative Example 1 was set as 100%, and was classified into the following ranks.

A: Improvement to less than 50% compared to Comparative Example 1 B: Improvement to 50% or more and less than 75% compared to Comparative Example 1 C: Improvement to 75% or more compared to Comparative Example 1 or less D: Deteriorated compared to Comparative Example 1

"Image density unevenness"
After adjusting the current value of the main charger so that the dark part potential at the developing unit position becomes a constant value, use a predetermined white paper for the original, and the image exposure light quantity so that the bright part potential at the developing unit position becomes the predetermined value Adjusted. Next, the halftone chart was placed on the 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. Therefore, the smaller the value, the better. The “image density unevenness” of each of the six electrophotographic photoreceptors prepared in Example 1 and Comparative Examples 1 and 2 was measured, and the average value between the six was measured for each of them, and compared with Comparative Example 1 for comparison. The value of Example 1 was set to 100%, and was classified into the following ranks.

A: Improvement to less than 50% compared to Comparative Example 1 B: Improvement to 50% or more and less than 75% compared to Comparative Example 1 C: Improvement to 75% or more compared to Comparative Example 1 or less D: Deteriorated compared to Comparative Example 1

"Electrophotographic characteristics variation evaluation method"
Each of the electrophotographic photoconductors prepared was installed in a Canon copier iR-5000 modified for this test, and the evaluation items were “chargeability variation” and “sensitivity variation”. Each item was evaluated by a specific evaluation method.

"Chargeability variation"
The “charging ability” of each of the six electrophotographic photoreceptors produced in Example 1 and Comparative Examples 1 and 2 at the middle position in the axial direction is measured. The difference between the maximum value and the minimum value with respect to the average value of the “chargeability” of the six electrophotographic photoreceptors is evaluated as “chargeability variation”. Therefore, the smaller the value, the better. Example 1 and Comparative Example 2 were compared with Comparative Example 1, and the value of Comparative Example 1 was set to 100%, and was classified into the following ranks.

A: Less than 75% compared to Comparative Example 1 B: 75% or more less than equivalent compared to Comparative Example 1 C: equivalent to Comparative Example 1 D: increased compared to Comparative Example 1

"Sensitivity variation"
The “sensitivity” of each of the six electrophotographic photoreceptors produced in Example 1 and Comparative Examples 1 and 2 is measured at the axial center position. The difference between the maximum value and the minimum value with respect to the average value of “sensitivity” of the six electrophotographic photoreceptors is evaluated as “sensitivity variation”. Therefore, the smaller the value, the better. Examples 1 and 2 were compared with Comparative Example 1, and the value of Comparative Example 1 was set to 100%, and was classified into the following ranks.

A: Less than 75% compared to Comparative Example 1 B: 75% or more less than equivalent compared to Comparative Example 1 C: equivalent to Comparative Example 1 D: increased compared to Comparative Example 1

  The results are shown in Table 2.

  As is apparent from Table 2, the apparatus used in Example 1, that is, between the power dividing unit 116 and the high frequency power transmission unit 117 in the power dividing container 115, and the upper lid 107 which is a conductive part of the reaction container. By installing the shield member 119, it was possible to suppress unevenness in electrophotographic photoreceptor characteristics and variations in electrophotographic photoreceptor characteristics between different cylinders.

[Example 2]
In this example, as in Example 1, in the plasma processing apparatus shown in FIG.
B) 50 MHz
C) 250 MHz
D) 300 MHz
In the same manner as in Example 1, an electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared using each of the high frequency power supplies 113 under the conditions shown in Table 1. A total of four types were created.

[Comparative Example 3]
In this example, instead of the vacuum processing apparatus of FIG. 1 used in Example 2, the plasma processing apparatus shown in FIG. 3 is used as in Comparative Example 1, and the oscillation frequency is a) to ni. )
B) 30 MHz
B) 50 MHz
C) 250 MHz
D) 300 MHz
Using each high-frequency power source, a total of four types of electrophotographic photoreceptors comprising a charge injection blocking layer, a photoconductive layer, and a surface layer were prepared under the conditions shown in Table 1, as in Comparative Example 1.

[Evaluation of Example 2 and Comparative Example 3]
“Electricity bus direction unevenness”, “sensitivity bus direction unevenness”, “image density” of the electrophotographic photoreceptors prepared in (a) to (d) of Example 2 and (a) to (d) of Comparative Example 3 For the above three items, (1) (b) of Example 2 and (b) of Comparative Example 3, (2) (b) of Example 2 and (b) of Comparative Example 3 ( 3) (c) of Example 2 and (c) of Comparative Example 3 and (4) (d) of Example 2 and (d) of Comparative Example 3 were respectively compared, and the value of Comparative Example 3 was taken as 100% It was divided into the following ranks. The results are shown in Table 3.

A: Less than 75% compared to Comparative Example 3 B: 75% or more less than equivalent compared to Comparative Example 3 C: equivalent to Comparative Example 3 D: increased compared to Comparative Example 3

  As is apparent from Table 3, when an electrophotographic photoreceptor is produced using a high frequency power source having an oscillation frequency of 50 MHz or more and 250 MHz or less, the effects of the present invention can be remarkably obtained, and the electrophotographic photoreceptor is obtained. Unevenness of characteristics can be suppressed.

[Example 3]
In this example, instead of the plasma processing apparatus of FIG. 1 used in Example 2, two high frequency power supplies 513A and 513B capable of supplying high frequency power of different frequencies were used as shown in FIG. An electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 4 with an oscillation frequency of the high frequency power source A: 513A being 105 MHz and an oscillation frequency of the high frequency power source B: 513B being 70 MHz. .

[Comparative Example 4]
In this example, the apparatus shown in FIG. 6 was used instead of the plasma processing apparatus of FIG. 5 used in Example 3. An electrophotographic photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was prepared under the conditions shown in Table 4 with an oscillation frequency of the high frequency power source A: 513A being 105 MHz and an oscillation frequency of the high frequency power source B: 513B being 70 MHz. .

[Evaluation of Example 3 and Comparative Example 4]
The “photosensitive busbar direction unevenness”, “sensitivity busbar direction unevenness”, and “image density unevenness” of the electrophotographic photoreceptor produced in Example 3 and Comparative Example 4 were evaluated, and the above three items were compared with Example 3. Example 4 was compared with each other, and the value of Comparative Example 4 was set to 100%, and was classified into the following ranks. The results are shown in Table 5.

A: Less than 75% compared to Comparative Example 4 B: 75% or more less than equivalent compared to Comparative Example 4 C: Equivalent compared to Comparative Example 4 D: Increased compared to Comparative Example 4

  As is apparent from Table 5, the effect of the present invention can be obtained even when two high-frequency power supplies 113A and 113B capable of supplying high-frequency power of different frequencies are used. Furthermore, when compared with the results of Example 2 and Comparative Example 3, as in this example, a plurality of high frequency power sources capable of supplying high frequency power of different frequencies are used, and a plurality of high frequency powers having different frequencies are superimposed. It can be seen that the effects of the present invention can be remarkably obtained and the unevenness of the characteristics of the electrophotographic photoreceptor can be suppressed.

1A and 1B are schematic cross-sectional views of an example of a plasma processing apparatus according to the present invention as seen from the side of an electrophotographic photoreceptor manufacturing apparatus using a plasma CVD method. 2A and 2B are enlarged views of the vicinity of the upper lid of the apparatus shown in FIG. 1 as an example of the plasma processing apparatus according to the present invention. 3A and 3B are schematic explanatory views of an example of a conventional plasma processing apparatus and an apparatus for manufacturing an electrophotographic photoreceptor by a plasma CVD method. FIG. 4A and FIG. 4B are schematic explanatory diagrams of an apparatus for manufacturing an electrophotographic photoreceptor by a plasma CVD method as an example of a conventional plasma processing apparatus. 5A and 5B are schematic cross-sectional views of an example of a plasma processing apparatus according to the present invention, as seen from the side of an electrophotographic photoreceptor manufacturing apparatus using a plasma CVD method. 6A and 6B are schematic explanatory views of an apparatus for manufacturing an electrophotographic photoreceptor by a plasma CVD method as an example of a conventional plasma processing apparatus.

Explanation of symbols

101 reaction vessel 102 base 103 source gas introduction means 104 rotation mechanism 105 base lower support means 106 base cap 107 upper lid 108 base heater 109 high frequency electrode 110 source gas introduction pipe 111 pressure measurement means 112 throttle valve 113 high frequency power supply 114 matching circuit 115 power Division container 116 Power division unit 117 Plural high frequency power transmission unit 118 Earth shield 119 Shield member 419 Coaxial cable 513A High frequency power source A
513B High frequency power supply B

Claims (7)

  In a plasma processing apparatus for performing plasma processing on a substrate installed in a reaction vessel, a matching circuit, a power dividing unit that divides high-frequency power after passing through the matching circuit into a plurality of high-frequency power transmission units, and the plurality of high-frequency waves A plurality of high-frequency electrodes connected to each of the power transmission units, the power dividing unit and the plurality of high-frequency power transmission units are included, and a power dividing container formed of a conductive member is provided, and the reaction container is at least partially A shield formed of a conductive member and formed of a conductive member between the power dividing unit and the plurality of high-frequency power transmission units and a conductive part of the reaction vessel forming a part of the power dividing vessel A plasma processing apparatus in which a member is installed.   The plasma processing apparatus according to claim 1, wherein at least a part of the reaction vessel is made of a dielectric member, and the high-frequency electrode is installed outside the reaction vessel.   3. The plasma processing apparatus according to claim 1, further comprising a high-frequency power source capable of supplying a high-frequency power having a frequency of the high-frequency power of 50 MHz to 250 MHz. 4.   The high-frequency power source includes a plurality of high-frequency power sources capable of supplying high-frequency power having different frequencies, and a power superimposing unit that superimposes a plurality of high-frequency powers having different frequencies is disposed between the matching circuit and the power dividing unit. The plasma processing apparatus according to claim 1, wherein the plasma processing apparatus is installed.   5. The plasma processing apparatus according to claim 1, wherein a conductive portion of the reaction vessel that forms a part of the power dividing vessel is not parallel to a deposition film formation surface of the substrate. 6. .   The plasma processing apparatus according to claim 1, wherein the base is cylindrical.   7. The plasma processing apparatus according to claim 1, wherein the plasma processing apparatus is used for forming a deposited film on an electrophotographic photosensitive member.

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