JPS6056427B2 - Manufacturing method of photoconductive member - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photoconductive member that is effective for forming a photoconductive layer on a predetermined support using glow discharge or the like.

Raw material for forming a photoconductive layer composed of an amorphous material containing silicon atoms as a matrix is introduced in a gaseous state into a deposition chamber that can be reduced in pressure, and is deposited on a desired support using a plasma phenomenon caused by glow discharge. When trying to form a photoconductive layer having the following characteristics, especially in the case of a large-area layer, it is important to ensure that the layer thickness and physical properties such as electrical, chemical, and photoelectric properties are uniform over the entire area. It is extremely difficult to increase the layer formation rate while achieving uniformity and quality, compared to ordinary vacuum evaporation methods.

For example, SiF or SiH.

and SiF. The mixed gas is decomposed using discharge energy to form a halogenated amorphous silicon (hereinafter a-Si: (X,H)) layer containing hydrogen atoms as necessary on the support. When trying to utilize the electrical properties of a layer, it is necessary to make the electrical properties uniform in the entire area of the layer and improve the layer quality, since the electrical properties of this layer greatly depend on the layer deposition rate and support temperature during layer formation. To measure this, it is necessary to reduce the layer deposition rate and increase the support temperature. On the other hand, from the point of view of improving productivity and mass production, it is conceivable to increase the discharge power and gas flow rate in order to increase the layer deposition rate.
Or, the layer formed when the gas flow rate is increased has a remarkable tendency to decrease the electrical, optical and photoconductive properties, and to increase the location dependence of these properties, forming a layer of good quality. The current situation is that this is extremely difficult.

Therefore, in order to industrialize the production of photoconductive members having a photoconductive layer made of an amorphous material with silicon atoms as the matrix, layer quality, which is closely related to photosensitivity, repeated use characteristics, and use environment characteristics, must be developed. It is necessary to improve productivity and mass production by maintaining uniformity and variation in characteristics, including reproducibility.The present invention has been made in view of the above points. It is extremely excellent in terms of productivity and mass production, and has excellent photoconductivity over a large area in terms of electrical, optical and photoconductive properties, layer quality, and bulk density and filling properties of the layer. It is an object of the present invention to also propose a method for manufacturing a photoconductive member that can easily obtain a layer.Also, the present invention aims to provide a method for manufacturing a photoconductive member that can easily obtain a layer.Also, even if the layer has a large area, the physical properties and layer thickness can be maintained over the entire area. A photoconductive layer that is substantially uniform and has excellent photoconductive and electrical properties in the usage environment, especially under humid and high temperatures, can be formed economically with high efficiency and high speed with good reproducibility. The purpose is also to propose manufacturing methods for parts.

The method for producing a photoconductive member of the present invention involves introducing a raw material for forming a photoconductive layer in a gaseous state into a deposition chamber that has been reduced to a desired pressure, and causing a discharge in the gas atmosphere of the raw material. In a method for manufacturing a photoconductive member in which a photoconductive layer is formed on a support for forming a photoconductive layer, the raw material has the general formula SimHexk (where M and k are positive integers, and ' is 0 or a positive integer'). +k=+2, X represents a halogen atom), and the ratio of these introduced into the deposition chamber is m higher than that of the compound with the lowest m. The method is characterized in that the raw material is introduced into the deposition chamber so that the content of the higher-order compound is 1V01% or more. The method for producing a photoconductive member of the present invention having such characteristics has significantly higher efficiency and speed than conventional methods, has excellent physical properties, optical properties, electrical properties, and photoelectric properties, and has excellent physical properties, optical properties, electrical properties, and photoelectric properties. The layer is dense and has a high degree of layer filling, and has excellent usage environment characteristics under humid and high temperatures.In addition, these characteristics and layer thickness are uniform over the entire area of the formed layer, and the layer is large in area. This can be economically and easily formed.

In particular, when the photoconductive member obtained by the manufacturing method of the present invention is applied to electrophotography, its properties can be utilized to the maximum extent possible.

In the present invention, when the compound represented by the general formula ImHexk is introduced into the deposition chamber for forming the photoconductive layer, it is introduced in a gaseous state from the viewpoint of ease of production and transportability of raw materials. Therefore, a material that is gaseous at room temperature and pressure, or at least easily gasified under layer forming/forming conditions, is used.

In the present invention, the compound represented by the general formula SlmHeXk is used as a raw material for producing Si (silicon) as constituent atoms constituting the photoconductive layer to be produced.

Examples of such raw materials used in the present invention include SiX4, Si2X6, Si3X8, and SiF.
IX3, SiH2X2, SiH3X (X is F, Ce, B
r, l), specifically SiF[4, SiCe
4, SiBr4, S114, S12F6, S12C16
, Si2Br6, Sj21 (3, S13F8, S13C
', SiHF'3, SiHCe3, SiF[Br3,S
iHl3, SiH2F2, SiH2Ce2, SiH3F
, SiH3C', etc.) which are in a gaseous state or can be easily gasified are effective examples.

In the present invention, a photoconductive layer is formed on a support by generating a gas discharge in a gas atmosphere of at least two compounds selected from the compounds represented by the above general formula. Among the selected compounds, m constitutes a higher order compound: Sj2F
Preferred examples include 6, sl2ce6, Si2Br6, and Si3F3, and these may be used in combination, or at least one of these may be used as the main component, and other compounds with higher m may be added. They can also be mixed to form a mixture of compounds with higher m.

In particular, as a compound where m constitutes a higher order, Sl2F
6, one or both of Si2Ce6, Si2Br6, or both of these as a main component, and m is the lowest order as a compound of SiF4, sjce4
A mixed system using the following is more preferable.

In the present invention, as a raw material for forming a photoconductive layer,
The ratio of at least two selected from among the compounds represented by the above general formula introduced into the deposition chamber is usually 1 for the compound with m of the lowest order, and the compound with m higher than this.
There are some systems that generate a discharge in a mixed gas atmosphere configured to have a voltage of V0e% or more, but the above ratio relationship is preferably 5V0e% or more, optimally 10V.
It is desirable that the content is 0e% or more.

As for the upper limit of the above ratio relationship, the optimal value is determined as desired depending on the type of compound constituting the raw material of the mixed system, but it is usually 99V0e%, preferably 97V0'%. It is desirable that this is the case.

In the present invention, when each of two or more compounds selected from the compounds represented by the above general formula is introduced into the deposition chamber, they are mixed in advance in the above ratio and then introduced into the deposition chamber. Alternatively, each may be separately introduced into the deposition chamber so as to maintain the above ratio.

In the present invention, Table 1 shows specific examples in which two or more of the compounds represented by the above general formula are used in combination.

Among the combination examples shown in Table 1, combination examples 1 to 10 are more preferred, particularly combination examples 1 to 3, and 5 to 8.
In the case of , a more significant effect is shown.

In the present invention, the mixed gas system of raw materials is mixed with atmospheric gas or other raw material gases for layer formation in order to obtain a predetermined concentration and gas pressure in a deposition chamber for forming a photoconductive layer. You can use it as well.

The atmospheric gas used in the present invention is one that does not have a negative effect on the photoconductive layer to be formed and is composed of atoms that become one of the constituent atoms of the layer, or one that is completely inert. will be adopted. Substances that can become such atmospheric gases include rare gases such as He, Ne, and Ar;
Fluorine, chlorine, bromine, iodine halogen gas, BrF,
ceF, ceF3, BrF5, BrF3, IF7, IF
5, gaseous or gasifiable interhalogen compounds such as ICe and IBr, hydrogen halide gases such as IIF', HCe and HBr, and H2.

Among these substances that become atmospheric gases, especially rare gases, H2
etc. can be used as effective ones.

Examples of other raw material gases for layer formation include substances that are in a gaseous state or can be easily gasified, and that contain impurity atoms as constituent elements that control the conductivity type of the photoconductive layer to be formed. In the method for manufacturing a photoconductive member of the present invention, when forming a photoconductive layer with the same characteristics and layer quality, the layer can be formed at a much higher speed and economically than the conventional method. Support temperature and discharge power can be significantly increased. For example, when obtaining a photoconductive layer having properties and layer quality that achieve the objectives of the present invention, the support temperature may be
The temperature can be set at 300° C. or higher and the discharge power can be set at 100 W or higher. Next, typical examples of photoconductive members formed by the method of manufacturing photoconductive members of the present invention are given.
The present invention will be further explained. FIG. 1 is a schematic structural diagram schematically showing an example of the structure of a typical photoconductive member obtained by the present invention.

A photoconductive member 100 shown in FIG. 1 can be applied to electrophotography or an imaging device, and includes an intermediate layer 102 provided as necessary on a support 101 for the photoconductive member; It has a layered structure composed of a photoconductive layer 103 provided according to the manufacturing method of the present invention.

The support 101 may be electrically conductive or electrically insulating.

Examples of the power transmitting support include NiCr, stainless steel, Af, Br, MO, Au, Ir, Nb, Ta, V, T.
Examples include metals such as i, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. .

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, its surface may be NiCr, Al, Cr, MO, Au,
Ir, Nb, Ta, V, Tj, Pt, Pd, ln2O,
, SnO2, ITO (Irl2O3+SnO2), etc., or if it is a synthetic resin film such as polyester film, NiCr
, Ae, Ag, Pb, Zn, Ni, Au, Cr, MO,
Metals such as Ir, Nb, Ta, ■, Ti, and Pt are processed by vacuum evaporation, electron beam evaporation, sputtering, etc. or laminated with the above-mentioned metal, and the surface thereof is subjected to conductive treatment.

The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. Statue! If used as a component for continuous high-speed copying, it is desirable to use an endless belt or cylindrical shape.
The intermediate layer 102 is made of a non-photoconductive amorphous material containing, for example, silicon atoms and carbon atoms, nitrogen atoms, or halogen atoms (X), and allows carriers to flow into the photoconductive layer 103 from the support 101 side. and prevents the passage of photocarriers generated in the photoconductive layer 103 and moving toward the support 101 from the side of the photoconductive layer 103 to the side of the support 101 due to the irradiation of electromagnetic waves. Some have the ability to easily forgive.

To form the intermediate layer 102, a glow discharge method is adopted because it can be performed continuously up to the formation of the photoconductive layer 103, but in that case, the raw material gas for forming the intermediate layer may be changed as needed. By mixing it with a diluting gas such as He or Ar at a predetermined mixing ratio and introducing it into a deposition chamber for vacuum deposition in which the support 101 is installed, a glow discharge is generated in the introduced gas atmosphere. The intermediate layer 102 may be formed on the support 101 by converting it into gas plasma.

Starting materials that can be effectively used as raw material gas for forming the intermediate layer 102 include SiH4, Sl2He, Si3H8, Si4H,
Silicon hydride such as silanes such as O, N
or N (5H) as a constituent atom, such as nitrogen (N2), ammonia (NH3), hydrazine (H2NNH2), hydrogen azide (HN3), ammonium azide (NH4N3), etc. Nitrogen compounds such as nitrogen, nitrides, and acyides that can be or are gasified, saturated hydrocarbons having 1 to 5 carbon atoms, such as saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 1 to 5 carbon atoms, and nitrogen compounds having C and H as constituent atoms. Specifically, saturated hydrocarbons such as 2 to 4 acetylenic hydrocarbons include methane (CH4), ethane (C2H6), propane (
C3H8), n-butane (n-C4HlO), pentane (C5Hl.

), ethylene hydrocarbons include ethylene (C2H4
), propylene (C3H6), butene-1 (C4H8)
, butene-2 (C4ll8), isobutylene (C4H8
), pentene (C5HlO), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (
C3H4), butene (C4FI6), etc. In addition to these, examples include oxygen (02), ozone (03), carbon monoxide (CO), carbon oxide (CO2), nitrogen monoxide (NO
), nitrogen dioxide (NO2), dinitrogen monoxide (N2O), etc. These starting materials for forming the intermediate layer 102 are appropriately selected and used during layer formation so that predetermined atoms are included in the formed intermediate layer 102 as constituent atoms.

Materials other than those mentioned above constituting the intermediate layer 102 include electrically insulating metal oxides.

The electrically insulating metal oxides constituting the intermediate layer 102 include TlO2, ce2O3, ZrO2, HfO2, Ge
O2, caO, BeO, p2O5, Y2O3, cr2O
3, Ae2O3, MgO, MgO-Al2O3SiO2
- MgO etc. can be mentioned as preferred.

Two or more of these may be used in combination to form the intermediate layer 102. can be mentioned.

Further, the intermediate layer 102 can also be formed by using aluminum or an aluminum alloy as the support 101 and subjecting the surface of the aluminum support or aluminum alloy support to alumite or boehmite treatment.

The thickness of the intermediate layer 102 is usually 30 to 10
00A1 is preferably 50 to 600A. The photoconductive layer 103 is an amorphous material a-Si, which has the semiconductor properties shown below, has silicon atoms as its base material, contains X, and optionally contains H: (X,H)
It consists of

1P type a-Si: (H,X)... Contains only acceptor.

Or one that contains both a donor and an acceptor and has a high acceptor concentration (Na). 5i type a-Si:
(H,X)...Na-Nd-O or Na-N
d's.

The thickness of the photoconductive layer 103 is appropriately determined as desired in accordance with the purpose of the application, such as a reading device, a fixed imaging device, or an electrophotographic image forming member.

The layer thickness of the photoconductive layer 103 shown in FIG. The thickness can be determined as appropriate and desired, and in normal cases, it is preferably several hundred to several thousand times or more thicker than the thickness of the intermediate layer 102.

The specific value is usually 1 to 100μ, preferably 2 to 100μ.
It is desirable that the thickness be in the range of 50μ.

The amount of X contained in the photoconductive layer of the photoconductive member shown in FIG. 1, or (H+X) when both H and X are contained.
It is desirable that the amount of is usually 1 to 40 at 0 mjc%, preferably 5 to 30 at 0 mic %.

In order to make the photoconductive layer 103 n-type or p-type, doping is performed while controlling the amount of n-type impurity, p-type impurity, or both impurities in the layer during layer formation. It is accomplished by doing.

The impurities doped into the photoconductive layer include elements of group A of the periodic table, such as B and A, as p-type impurities.
Suitable examples include e, Ga, In-Te, etc.
Suitable n-type impurities include elements of Vly<A of the periodic table, such as N, P, AS, Sb, and Bl, with B, Ga, P, and S being particularly suitable. . In the present invention, the photoconductive layer 103 has a desired conductivity type.
The amount of impurities to be doped into the inside is determined as appropriate depending on the desired electrical and optical properties, but it is determined according to the
In the case of group A impurities, it is sufficient to dope in an amount range of 3 x 10-2 at0 mic% or less, and it is suitable for group A of group A of the periodic table.
In the case of impurities, doping may be carried out in an amount range of 5×10 −3 at0 mic % or less.

In order to dope an impurity into the photoconductive layer 103, a raw material for impurity introduction may be introduced in a gaseous state into a deposition chamber together with the main raw material for forming the photoconductive layer 103 during layer formation.

As the raw material for introducing such impurities, those that are in a gaseous state at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions, are employed. Specifically, starting materials for introducing such impurities include PH3, P2H4, PF3,
PF5, PC'3, ASH3, ASF3, ASF5, A
SCe3, SbH3, SbF5, BiH3, BF3, B
Ce3,BBr3,B21-16,B4H10,j8H
99B5Hll9B6HlO9B6Hl29AfC'3
I can name 9 etc.

Example 1 Using the apparatus shown in FIG. 2 installed in a completely shielded clean room, an electrophotographic image forming member was prepared by the following operations.

0.5w with clean surface! A molybdenum (substrate) 202 with a thickness of n and 10 CWi square was firmly fixed to a fixing member 203 at a predetermined position in the deposition chamber 201 . target 205,
206 is a structure in which polycrystalline high purity silicon (99.999%) is placed on high purity graphite (99.999%). The substrate 202 is heated with an accuracy of ±0.5° C. by a heater 204 inside the fixing member 203. Temperature was measured directly on the backside of the substrate by a thermocouple (Almeru Cromel). Next, after confirming that all valves in the system are closed, close main valve 2.
31 was once evacuated to about 5 x 10-7 t0rr (at this time, all valves in the system were closed),
Auxiliary valve 229 and outflow valves 224, 225, 2
28 is opened and the flow meters 237, 238, 241 are sufficiently degassed, the outflow valves 224, 225, 2 are opened.
28 and auxiliary valve 229 were closed.

Open the valve 218 of the Ar (99.999% purity) gas cylinder 213, and the outlet pressure gauge 236 reads 1k9/CI.
After adjusting to L, the inflow valve 223 was opened, and then the outflow valve 228 was gradually opened to allow Ar gas to flow into the chamber 201. The outflow valve 22 is closed until the reading on the Pirani gauge 242 becomes 5-0-4t0rr.
8 is gradually opened, and after the flow rate is stabilized in this state, the main valve 231 is gradually closed, and the indoor pressure is reduced to 1×.
The aperture was narrowed down to 10-2t0rr. After opening the shutter 208 and confirming that the flow meter 241 is stable, the high frequency power source 243 is turned on and the 13
．． AC power of 56 MHz and 100 W was input. Under these conditions, the layers were formed while making matching so that stable discharge could continue. Continue discharging in this way for 1 minute and
An intermediate layer having a thickness of 0A was formed. Thereafter, the high frequency power supply 243 was turned off, and the discharge was temporarily stopped. Subsequently, the outflow valve 228 and inflow valve 223 are closed, and the main valve 231 is completely closed to remove the gas from the chamber 201.
Vacuum was applied to -7t0rr. After that, the heater 204 -
The input voltage was increased, and the input voltage was varied while detecting the substrate temperature until it stabilized at a constant value of 400°C. Then the auxiliary valve 229 and then the outflow valve 228
Regarding everything, the inside of the flow meter 241 is also well maintained. A degassed vacuum was applied.

After closing the auxiliary valve 229 and the outflow valve 228, B2
Sl2F6 gas containing 10v'01ppm of H6 (hereinafter referred to as B
It is abbreviated as 2H6/Sl2F6. (purity 99.999%) valve 214 of cylinder 209, SiF4 gas (purity 99.9%)
99%) Open the valve 215 of the cylinder 210 and set the pressure of the outlet pressure gauges 232 and 233 to 1k9/c! Adjust to t,
Gradually open the inflow valves 219, 220, 223 and inject B2H6/Sj into the flow meters 237, 238, 241.
2F6 gas, SiF4 gas, and -Ar gas were respectively introduced. Subsequently, the outflow valves 224, 225, 228 were gradually opened, and then the auxiliary valve 229 was gradually opened.
At this time, the inflow valves 219, 220, and 223 were adjusted so that the ratio of the B2H6/Si2F6 gas flow rate, the SiF4 gas flow rate, and the Ar gas flow rate was 30:1:69. Next, while watching the reading on the Pirani gauge 242, adjust the opening of the auxiliary valve 229 so that the inside of the chamber 201 is 0-2t0r.
The auxiliary valve 229 was opened until r. After the internal pressure of the chamber 201 becomes stable, the main valve 231 is gradually closed.
The opening was narrowed until the reading on the Pirani gauge 242 reached 0.2t0rr. After confirming that the gas inflow was stable and the internal pressure was stable, the shutter 208 (which also served as an electrode) was closed, and then the high-frequency power supply 243 switch was turned on. Set it to 0N state,
High frequency power of 13.56 MHz was applied between the electrode 203 and the shutter 208 to generate glow discharge in the chamber 201, resulting in an input power of 150 W. After continuing the glow discharge for one hour to form a photoconductive layer, the heating heater 204 is turned to C.
The high frequency power supply 243 is also set to 0FF state,
After the substrate temperature reaches 100°C, the outflow valves 22 225, 228 and the inflow valves 219, 220,
223 and fully open the main valve 231 to open the chamber 20.
1 to below 10-5t0rr, the main valve 23
1 was closed, the inside of the chamber 201 was brought to atmospheric pressure by the leak valve 230, and the substrate was taken out. In this case, the total thickness of the layer formed was approximately 20 microns. The image forming member thus obtained was placed in a charging exposure experiment apparatus, and was heated to 0.2
Corona charging was performed for sec, and a light image was immediately irradiated. The optical image was created using a tungsten lamp light source at 1.5eUX.
A light amount of SeC was irradiated through a transmission type test chart. Immediately thereafter, a good toner image was obtained on the surface of the member by cascading a developer (containing toner and carrier) with a chargeability of ◯ on the surface of the member.

When the toner image on the member was transferred onto transfer paper by corona charging at 15.0 K, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained. Next, the above-mentioned image forming member was exposed to light for 0.2 sec at E5.5 Kv using a charging exposure experiment device.
Immediately after performing corona charging between was gotten. From this result and the previous results, it was found that the electrophotographic image forming member obtained in this example had no dependence on charging polarity and had the characteristics of a bipolar image forming member.

Example 2 After forming an intermediate layer on a molybdenum substrate under the same operations and conditions as in Example 1, the intermediate layer was formed on a molybdenum substrate under the same operations and conditions as in Example 1, using the gas types and relative flow rates as shown in Table 2. A photoconductive layer was formed on the intermediate layer.

When a toner image was formed using the image forming member thus obtained in the same manner as in Example 1, sample A had a voltage of 05.5 KV.
A better toner image was obtained with the combination of corona charging, image exposure, and 1-chargeable toner. On the other hand, sample B
Conversely, 46.0KV corona charging, then image exposure,
A better toner image was obtained with the combination of θ-chargeable toners.

Example 3 After forming an intermediate layer on a molybdenum substrate using the same operations and conditions as in Example 1, the types of gases were changed as shown in Table 3 (by increasing the number of cylinders in Figure 2 as necessary). A photoconductive layer was formed on the intermediate layer under the same operation and conditions as in Example 1 with respect to the relative flow rate.

As a result of examining the image forming member obtained in this way from the viewpoint of productivity (deposition rate) and characteristics (image quality in high temperature and high humidity, repeated operation), it was found that in order to achieve the object of the present invention, it is necessary to use a mixed raw material. Among the gases, the compound represented by the above general formula has the lowest n, and the higher-order compound is 1■o1
It has been found that it is necessary to form the photoconductive layer so that the content is %.

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 is a schematic diagram for explaining the layer structure of one embodiment of a photoconductive member produced by the manufacturing method of the present invention, and FIG. FIG. 2 is a schematic explanatory diagram showing an example of a device for realizing the. 100... Photoconductive member, 101... Support, 102
... Barrier layer, 103 ... Amorphous layer.

Claims (1)

[Claims] 1. A raw material for forming a photoconductive layer is introduced in a gaseous state into a deposition chamber that is reduced to a desired pressure, and a discharge is generated in the gas atmosphere of the raw material, thereby forming a layer on a support for forming a photoconductive layer. In the method for manufacturing a photoconductive member in which a photoconductive layer is formed on a substrate, the raw material has the general formula SimHlXk (where m
, k is a positive integer, l is 0 or a positive integer, and l+k=2m+2
, X represents a halogen atom), and the proportion of these compounds introduced into the deposition chamber is m higher than that of the compound with the lowest m
A method for producing a photoconductive member, characterized in that the raw material is introduced into the deposition chamber so that the content of the higher-order compound is 1 vol % or more.