JPH0550743B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a method for manufacturing an electrophotographic photoreceptor and an apparatus for manufacturing the same. <Prior art> For example, vacuum evaporation,
Plasma CVD method, CVD method, reactive sputtering method, ion plating method, optical CVD method, etc. have been tried, and in general, plasma CVD
Laws are widely used and corporatized. However, the amount of light received by amorphous silicon depends on its electrical and optical properties, its fatigue properties during repeated use, its use environment properties, and its uniformity.
There is room for further improvement in overall characteristics in terms of productivity and mass production, including reproducibility. The reaction process for forming an amorphous silicon photoreceptive layer using the conventional plasma CVD method, which has been widely used, is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is still unclear. There were quite a few. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant effect on the deposited film formed. Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, in order to develop a photoreceptive layer made of amorphous silicon that has electrical and optical properties that fully satisfy various uses, it is currently considered best to form it by plasma CVD. . However, in the case of electrophotographic photoreceptors, it is necessary to fully satisfy the requirements of large area, uniformity of film thickness, and uniformity of film quality, and mass production with reproducibility. Forming an amorphous silicon-based photoreceptive layer using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production are also complex, with a narrow management tolerance and equipment adjustments. However, these issues have been pointed out as issues that should be improved in the future. On the other hand, with conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained. As mentioned above, in forming an amorphous silicon-based photoreceptive layer, there is a strong desire to develop a formation method that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. These are the layers constituting other photoreceptive layers,
For example, the same can be said of silicon nitride films, silicon carbide films, and silicon oxide films. The present invention eliminates the drawbacks of the photoreceptive layer formed by the plasma CVD method described above, and at the same time provides a novel method for producing an electrophotographic photoreceptor and an apparatus that does not involve conventional forming methods. <Objective and Summary of the Invention> The object of the present invention is to maintain the characteristics of the formed film and reduce the deposition rate without using a plasma reaction in a film forming space for forming a photoreceptive layer for electrophotography. The objective is to simplify the management of film formation conditions and easily achieve mass production of films while improving the performance of the film. The method for manufacturing an electrophotographic photoreceptor of the present invention includes introducing a precursor used for forming a photoreceptive layer and an active species that chemically reacts with the precursor into a film forming space. A method for producing an electrophotographic photoreceptor in which a photoreceptive layer is formed on an electrophotographic substrate disposed on the electrophotographic substrate, wherein the active species is transferred to the film forming space through a first transport space that communicates with the film forming space on the downstream side. The precursor has an opening to the first transport space, and a second transport space provided in the first transport space and communicating with the film forming space.
It is characterized in that the film is introduced into the film forming space through the transportation space of each of the above. Further, the electrophotographic photoreceptor manufacturing apparatus of the present invention includes:
A precursor used for forming a photoreceptive layer and an active species that chemically reacts with the precursor are introduced into a film forming chamber to form a photoreceptive layer on an electrophotographic substrate placed in the film forming chamber. An apparatus for manufacturing an electrophotographic photoreceptor, comprising: a first transport path; an activation space provided upstream of the first transport path for generating the active species;
having an opening to the first transport path;
a second transport route provided inside the transport route;
characterized by having a precursor forming space for generating the precursor provided upstream of the opening of the transport path, and a film forming chamber communicating with each of the first and second transport paths. . As described above, in the present invention, a film forming space in which a desired electrophotographic photoreceptive layer is formed and a space in which precursors and active species are generated are separated, and the precursor and active species are separated. Since the spaces in which these are generated are different, and plasma discharge is not used in the film-forming space, control of film-forming conditions becomes extremely easy, and layer quality can be easily managed. In the present invention, active species are introduced into the film forming space through the transport space (A), and precursors are introduced into the film forming space through the transport space (B). The residence time of the precursor in the transport space (A) can be set as appropriate by varying the opening position in the transport space (A). In this case, the transport speed in the precursor transport space (B) can also be selected as one of the control parameters for controlling the residence time. In the present invention, the transportation space (A) and the transportation space
The opening position to the film forming space (B) is determined as appropriate depending on the lifetime of the active species and the precursor. In the case of the present invention, since a precursor with a relatively long life is used and an active species with a short life compared to the precursor is used, the opening position of the transport space (A) to the film forming space is is preferably closer to the film forming space. It is desirable that the opening of the transport space (A) to the film forming space and the opening of the transport space (B) to the transport space (A) be shaped like a nozzle or an orifice. In particular, in the case of a nozzle-shaped nozzle, by positioning the nozzle opening near the film-forming surface of the substrate placed in the film-forming space, the film-forming efficiency and effective raw material consumption rate can be significantly increased. I can do it. In the present invention, activated species are generated in an activation space that communicates upstream with the transport space (A), and precursors are generated in a precursorization space that communicates with the transport space (B) upstream. However, the present invention is not limited to these. For example, the transport space (A) can also be used as an activation space, and the transport space (B) can also be used as a precursor formation space. In particular, when both transport spaces serve as an activation space and a precursor forming space, the same means can serve as both the activation means and the precursor forming means without having to provide them separately. For example, by making the transport space (A) and the transport space (B) have a double glass tube structure and installing a microwave plasma device around the outer glass tube, it is possible to activate the plasma at the same position in the transport direction. Seeds and precursors can be generated simultaneously. In the present invention, a transportation space (A) and a transportation space (B),
Preferably, the open opening portion is located inside the film forming space. In the present invention, the transportation space (A) and the transportation space
A double space structure consisting of a transport space (B) provided inside (A) is not limited to one, but a plurality of them can be provided in the film forming apparatus to introduce each double space structure into each double space structure. By varying the types of active species and precursors, deposited layers with different properties can be formed on the substrate disposed within the deposition space. In this case, for example, the formation of each of the deposited layers can be started separately and simultaneously at different positions on the substrate, or the deposited layer (A) is first formed on the substrate, then the deposited layer (B), It is also possible to form a layered structure in which N layers of deposited layers are laminated in order (C)...(N). Specifically, a photoreceptive layer for electrophotography includes, in order from the substrate side, a charge injection prevention layer, a photoconductive layer, and a photoconductive layer.
In the case of a three-layer structure of the surface layer, first, a charge injection prevention layer is formed on the substrate using the double space structure (A), and then the double space structures (B) and (C) are formed. By using each of them, a photoconductive layer and a surface layer can be sequentially formed on a previously formed layer. Of course, in this case, the formation of each layer does not only involve starting the formation of the next layer after the formation of each layer on the entire surface of the substrate is completed;
By simply delaying the start of the formation of each layer for a desired period of time, it is possible to form each layer simultaneously in terms of time, although the formation of each layer may be delayed locally. The formation of each layer can be performed in separate deposition spaces, but if the features of the present invention are to be utilized to the fullest, it is possible to form layers with different characteristics simultaneously in the same deposition space. Each of the layers can be formed. Furthermore, according to the method of the present invention, unlike the conventional plasma CVD method, the film-forming space, the activation space, and the precursor-forming space are separated from each other, so that contaminants from the inner walls of the film-forming space and A feature of this method is that the influence of residual gas remaining in the film forming space can be substantially eliminated. The term "precursor" in the present invention refers to something that can serve as a raw material for a deposited film to be formed, but is completely or almost incapable of forming a deposited film in its current energy state. "Active species" are capable of chemically interacting with the precursor to, for example, impart energy to the precursor, or chemically reacting with the precursor to form a deposited film of the precursor. It refers to something that has the role of making things possible. In other words, the precursor according to the present invention does not form a deposited film by itself, but is in a state where a deposited film can be formed by energy provided by the active species or by chemical reaction with the active species. Therefore, the active species may include constituent elements constituting the deposited film to be formed.
Alternatively, such a component may not be included. In the present invention, the precursor from the transport space introduced into the film forming space has a lifetime of preferably 0.01 seconds or more, more preferably 0.1 seconds or more, and optimally 1 second or more, but the lifetime may be selected as desired. has been used,
The constituent elements of this precursor constitute the main components constituting the deposited film formed in the film forming space.
The active species introduced into the film forming space from the transport space (A) preferably has a lifetime of 10 seconds or less, more preferably 8 seconds or less, and optimally 5 seconds or less.
When forming a deposited film in the film forming space, these active species are simultaneously introduced into the film forming space from the transport space (B) and chemically interact with the precursors containing the constituent elements that will be the main constituents of the deposited film to be formed. interact with (i.e., impart energy to the precursor, as described above,
It is brought into a state where it can chemically react with the precursor to form a deposited film. ). As a result, a desired deposited film can be easily formed on a desired substrate. According to the method of the present invention, the deposited film that is formed without generating plasma in the film forming space is not adversely affected by etching action or other adverse effects such as abnormal discharge action. Furthermore, according to the present invention, by controlling the atmospheric temperature and substrate temperature of the film forming space as desired,
A more stable CVD method can be achieved. One of the points in which the method of the present invention differs from conventional CVD methods is that it uses active species and precursors that are generated in advance in a space different from the film forming space. This makes it possible to dramatically increase the deposition rate compared to conventional CVD methods, and at the same time obtain a film of high quality.In addition, the temperature of the substrate during the formation of the deposited film is further reduced. This makes it possible to provide deposited films with stable film quality in large quantities industrially and at low cost. In the present invention, the activated species generated in the activation space (A) are not only generated by energy such as electric discharge, light, heat, etc., or by a combination of these, but also by contact with a catalyst, etc. Alternatively, it may be produced by addition. In the present invention, the raw material introduced into the precursorization space (B) to produce a precursor is one in which an atom or atomic group with high electron-withdrawing property, or a polar group is bonded to a silicon atom. used. Examples of such things include SinX ₂ n ₊₂ (n=1, 2, 3..., X=F, Cl, Br, I), (SiX ₂ )n (n≧3, X=F, Cl , Br, I), SinHX ₂ n ₊₁ (n=1, 2, 3..., X=F, Cl, Br, I), SinH ₂ X ₂ n (n=1, 2, 3..., X =F, Cl, Br, I), etc. Specifically, for example, SiF ₄ , (SiF ₂ ) ₅ , (SiF ₂ ) ₆ ,
(SiF ₂ ) ₄ , Si ₂ F ₆ , SiHF ₃ , SiH ₂ F ₂ , SiCl ₄
(SiCl ₂ ) ₅ , SiBr ₄ , (SiBr ₂ ) ₅ and the like may be in a gaseous state or can be easily gasified. or,
SiH ₂ (C ₆ H ₅ ) ₂ , SiH ₂ (CN) ₂ and the like may also be used depending on the purpose of the deposited film to be formed. A precursor is generated by adding activation energy such as heat, light, or electric discharge to the above-mentioned material in a precursorization space. In the present invention, a precursor and an active species are mixed in the transport space (A), and the mixed gas is introduced into the film forming space. The mixed precursor and active species chemically interact to form a deposited film on a substrate previously placed in the film forming space. At this time, if necessary, the deposition rate is accelerated by applying energy such as heat or light directly into the film forming space or onto the substrate, and the desired deposited film can be efficiently formed. In the present invention, the raw materials introduced into the activation space to generate active species include H ₂ , SiH ₄ , SiH ₃ F,
In addition to SiH ₃ Cl, SiH ₃ Br, SiH ₃ I, etc., He, Ne,
Examples include rare gases such as Ar. In the present invention, the ratio between the amount of precursor and the amount of active species when mixed in the transport space (A) can be determined as desired depending on the deposition conditions, the types of precursor and active species, etc. , preferably 100:1 to 1:100 (flow rate ratio)
is suitable, and more preferably 10:1 to 1:10. Moreover, in the present invention, the transport space (B) into the transport space (A)
The position of the opening of the transport space (A) to the film forming space is preferably 0.1 mm to 200 mm, more preferably 1 mm to 100 mm. In the present invention, excitation energy such as discharge energy, thermal energy, light energy, etc. is used as the energy for generating precursors and active species, taking into consideration the respective conditions and equipment. <Example of Embodiment> Next, the present invention will be explained by giving a typical example of an electrophotographic photoreceptor formed by the deposited film manufacturing method of the present invention. FIG. 1 is a diagram for explaining an example of the configuration of a typical electrophotographic photoreceptor obtained by the present invention. An electrophotographic photoreceptor 100 shown in FIG. 1 has a photoconductive layer 10 on a support 101 for electrophotography.
3, an intermediate layer 102 and a surface layer 104 provided as necessary. The support 101 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au, Ir,
Examples include metals such as Nb, Ta, V, Ti, 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, 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, Ti, Pt, Pd,
If it is conductive treated by providing a thin film of In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +SnO ₂ ), or a synthetic resin film such as polyester film,
NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo,
Vacuum evaporation of metals such as Ir, Nb, Ta, V, Ti, Pt, etc.
The surface is made conductive by processing by electron beam evaporation, sputtering, etc., or by laminating with the metal. The shape of the support body is cylindrical,
It can be formed into any shape such as a belt or a plate, and its shape is determined as desired. For example, in the case of continuous high-speed copying, it is preferably an endless belt or a cylinder. The intermediate layer 102 is made of, for example, silicon atoms, carbon atoms, nitrogen atoms, oxygen atoms, or halogen atoms (X).
is composed of a non-photoconductive amorphous material containing a carrier that effectively prevents carriers from flowing into the photoconductive layer 103 from the side of the support 101 and generated in the photoconductive layer 103 by irradiation with electromagnetic waves, Support 10
It has a function of easily allowing the photocarrier moving toward the photoconductive layer 103 to pass from the photoconductive layer 103 side to the support 101 side. When forming the intermediate layer 102, the photoconductive layer 1
The process can be carried out continuously up to the formation of 03. In that case, the raw material gas for forming the intermediate layer may be mixed with a diluent gas such as He or Ar at a predetermined mixing ratio, if necessary. First, a raw material gas for active species generation is introduced into the activation space, and activation energy is applied to generate active species in the activation space, thereby forming an atmosphere containing the active species, and transferring the activated species to the transport space (A). transport. On the other hand, the precursor generated in the precursorization space is transported through the transport space (B), discharged into the transport space (A), and mixed with the active species. The mixed precursor and active species chemically interact. The mixed gas containing the precursor and active species is transferred to the support 10
The intermediate layer 102 is formed on the support 101 by applying film-forming energy to these components as necessary. That's fine. The effective starting materials for generating the active species introduced into the activation space (B) to form the intermediate layer 102 are:
Ar, He, H ₂ , SiH ₄ whose constituent atoms are Si and H,
Hydrogen-rich halogenated silanes such as SiH ₃ Cl, SiH ₃ F, and SiH ₃ Br, nitrogen (N ₂ ), ammonia (NH ₃ ), Hydrazine (H ₂ NNH ₂ ), hydrogen azide (NH ₃ ), ammonium azide (NH ₄ N ₃ )
gaseous or gasifiable nitrogen, nitrogen compounds such as nitrides and azides, etc., saturated hydrocarbons having 1 to 5 carbon atoms, such as carbon atoms containing C and H, and 2 carbon atoms.
-5 ethylene hydrocarbons, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), and ethylene hydrocarbons such as
Ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), putene-1 (C ₄ H ₈ ), putene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ H ₆ ), and in addition to these, for example, oxygen (O ₂ ), Examples include ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrogen monoxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen monoxide (N ₂ O). These starting materials for forming the intermediate layer 102 include predetermined atoms as constituent atoms of the intermediate layer 1 to be formed.
02, they are appropriately selected and used during layer formation. On the other hand, effective starting materials that can be introduced into the precursorization space to generate a precursor when forming the intermediate layer 102 include SiF ₄ , SiH ₂ F ₂ , etc. easily by the action of energy
Produces long-lived precursors such as SiF ₂ . The thickness of the intermediate layer 102 is preferably 30~
The thickness is desirably 1000 Å, more preferably 50 to 600 Å. The photoconductive layer 103 is made of silicon atoms as a matrix so as to have photoconductive properties that allow it to fully function as an electrophotographic image forming member.
It is composed of amorphous silicon A-Six(H) containing halogen (X) and optionally hydrogen atoms (H). Similarly to the intermediate layer 102, the photoconductive layer 103 is formed by introducing a raw material gas such as H ₂ , SiH ₄ , or SiH ₃ F into the activation space (B) and generating active species with a predetermined activation energy. filled within the transport space. The activated species generated inside the activation space are transferred to the transport space (A).
is introduced into the film forming space through. On the other hand, starting materials for producing precursors such as SiF ₄ and SiF ₂ H ₂ are introduced into the precursor forming space, and activation energy is applied to these materials to produce precursors. The precursor mixes the active species downstream from the opening position through the transport space (B) to cause chemical interaction. A mixed gas consisting of a precursor and an active species is introduced into the film forming space, and a deposited film is formed on the substrate that has been placed in the film forming space in advance. As a result, the desired photoconductive layer 103 is deposited.
The thickness of the photoconductive layer 103 is appropriately determined according to the purpose of application. The thickness of the photoconductive layer 103 shown in FIG. 1 is set appropriately in relation to the thickness of the intermediate layer 102 so that the functions of the photoconductive layer 103 and the functions of the intermediate layer 102 are each effectively utilized. It can be determined according to desire, and in normal cases, it is preferably several hundred to several thousand times or more thicker than the layer thickness of the intermediate layer 102. As a specific value, preferably 1 to 100μ,
More preferably, it is in the range of 2 to 50μ. The amount of H contained in the photoconductive layer of the electrophotographic photoreceptor shown in FIG. 1 or the sum of the amounts of H and X is (X=F
(e.g. halogen atoms) preferably 1 to 40 atomic%,
More preferably, it is 5 to 30 atomic%. As for the amount of X alone, the lower limit is preferably
It is desirable that the content be 0.001 atomic %, more preferably 0.01 atomic %, most preferably 0.1 atomic %. The surface layer 104 of the electrophotographic photoreceptor shown in FIG. 1 is formed in the same manner as the intermediate layer 102 and the photoconductive layer 103, if necessary. If it is a silicon carbide film, for example, SiH ₄ , CH ₄ and H ₂ or
SiH ₄ and SiH ₂ (CH ₃ ) ₂ are introduced, and activation energy is applied to generate active species. On the other hand, a raw material gas for producing a precursor such as SiF ₄ gas is introduced into the precursor forming space, and a precursor is produced by the action of activation energy. The active species and precursors are
They are introduced into the film forming space (A) while being mixed and chemically interacting with each other. A surface layer 104 is then deposited. Further, as the surface layer 104, silicon nitride,
A deposited film with a wide bandgap such as a silicon oxide film is preferable, and is suitable for forming layers from the photoconductive layer 103 to the surface layer 104.
It is also possible to continuously change the umbilical membrane composition. The layer thickness of the surface area 104 is preferably 0.01μ
A range of ~5μ, more preferably 0.05μ to 1μ is desirable. In order to make the photoconductive layer 103 n-type or p-type as necessary, the amount of n-type impurity, p-type impurity, or both impurities is controlled in the formed layer during layer formation. However, it is achieved by doping. Suitable impurities to be doped into the photoconductive layer include elements of group A of the periodic table, such as B, Al, Ga, In, and Tl, as p-type impurities, and as n-type impurities. Preferred examples include elements of group A of the periodic table, such as N, P, As, Sb, Bi, etc., but especially B, Ga,
P, Sb, etc. are optimal. In the present invention, the amount of impurities doped into the photoconductive layer 103 in order to have a desired conductivity type is appropriately determined depending on the desired electrical and optical properties. In case of impurity A, 3×
Doping may be done in an amount range of 10 ^-2 atomic % or less, and in the case of impurities in group A of the periodic table, doping may be done in an amount range of 5×10 ^-3 atomic % or less. In order to dope impurities into the photoconductive layer 103, a raw material for impurity introduction may be introduced in a gaseous state into the activation space or the precursorization space during layer formation. At that time, it is introduced together with either the precursor raw material gas or the active species raw material gas. As the raw material for introducing such impurities, those that are in a gaseous state at room temperature and normal pressure, or that can be easily gasified at least under layer-forming conditions, are employed. Specifically, starting materials for introducing such impurities include PH ₃ , P ₂ H ₄ , PF ₃ , PF ₅ , PCl ₃ , AsH ₃ ,
AsF ₃ , AsF ₅ , AsCl ₃ , SbH ₃ , SbF ₅ , BiH ₃ ,
BF ₃ , BCl ₃ , BBr ₃ , B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ ,
Examples include B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , AlCl ₃ and the like. Example 1 Using the apparatus shown in FIG. 2, a drum-shaped electrophotographic image forming member was produced by the following operations. In Fig. 2, 201 is a film forming chamber (A), 202 is an activation chamber (B), 203 and 204 are walls for introducing activation energy and releasing raw material gas for active species, and 205 is for forming a deposited film. precursor raw material gas discharge pipe, 2
06 is a microwave power source which is an activation energy source, 207 is an Al cylinder for forming a deposited film, 2
08 is Al cylinder heater, 209 is
A motor for rotating the Al cylinder, 210 an exhaust valve, 211 a pipe for introducing a raw material gas for forming a deposited film, and 212 a pipe for introducing a raw material gas to be an active species. 213 is from the activation chamber (B) to the film formation chamber (A)
This is a nozzle for introducing the active species and the precursor mixed gas into the reactor. In this embodiment, the raw material gas introduction pipe 20
The position of the tip of No. 5 was set at about 7 cm from the nozzle 213. The Al cylinder 207 was suspended in the film forming chamber (A) 201, the exhaust valve 210 was opened, and the film forming chamber (A) and the activation chamber (B) were brought to a vacuum level of about 10 ^-5 torr. Next, the motor 209 is rotated and the heating heater 208
The Al cylinder temperature was maintained at approximately 300°C. first,
A raw material gas for depositing the charge injection blocking layer was introduced into the activation chamber (B). A mixed gas of H ₂ and B ₂ H ₆ (B ₂ H ₆ /H ₂ =
3000ppm) 50SCCM was introduced. SiF ₄ (100%) is introduced into the activation chamber (B) as a raw material gas for precursor generation.
Introduced 100SCCM. After the flow rate stabilizes, adjust the exhaust valve 210 to reduce the internal pressure of the film forming chamber (A) to approximately
It was set to 0.002Torr. After the internal pressure becomes constant, the microwave power supply 206 is operated to supply 200W to the activation chamber.
discharge energy was input. Keep this state for 1 hour to act as a charge injection blocking layer.
Al cylinder 207 in the deposition chamber (A) 201 for P ⁺ layer
deposited on top. After depositing the P ⁺ layer as an electricity injection blocking layer, stop the discharge in the activation chamber (B) and stop the introduction of B ₂ H ₆ .
The flow rate of H ₂ gas was set to 300 SCCM, and the flow rate of SiF ₄ gas was set to 300 SCCM. The internal pressure of the activation chamber (B) was set to 0.002 torr, and a discharge energy of 300 W was applied. This state was maintained for 2 hours and 30 minutes to deposit a photosensitive layer of 20 μm. Next, as raw materials for active species, the flow rate of H ₂ gas was set at 100 SCCM, the flow rate of CH ₄ was set at 300 SCCM, and as the raw material gas for precursors, SiF ₄ was set at 10 SCCM.
The internal pressure was 0.002Torr and the discharge energy was 200W. This state was maintained for 30 minutes to deposit a surface layer of about 5000 Å. In this way, a blocking type drum-shaped electrophotographic image forming member was produced. When the electrophotographic properties of this electrophotographic image forming member were examined, it was found that the properties were sufficient for practical use. Example 2 Using the apparatus shown in FIGS. 3 and 4, a drum-shaped electrophotographic image forming member was produced by the following operations. FIG. 3 shows the activation chambers 407 and 4 in FIG.
08,409 is described in detail. 301 is an activation chamber, 302 is a pipe for introducing raw material gas of a precursor, 303 is a microwave power source for activating the activation chamber, 304 is a pipe for introducing raw material gas of active species, and 305 is a pipe for introducing raw material gas of active species. A flow rate adjustment valve 306 is a flow rate adjustment valve for the precursor source gas, and 307 is a pipe for introducing the precursor source gas. FIG. 4 shows an apparatus for producing drum-shaped electrophotographic imaging members. The device in Figure 4 is
The activation chamber shown in the figure is 407, 408, 409 3.
A room has been set up. 409 is an activation chamber for depositing a P ⁺ layer which serves as a charge injection blocking layer. 408 is an activation chamber for photosensitive layer deposition. 407 is an activation chamber for depositing a surface charge injection blocking layer. 401 is a film forming chamber, 402 is an Al cylinder, 403 is an infrared lamp for heating the Al cylinder, 404 is a reflector for the infrared lamp, 405 is a motor for rotating and vertically driving the Al cylinder, and 406 is the Al cylinder and motor. The connecting shaft 410 is an exhaust valve. The Al cylinder 402 is attached to the rotating shaft 406 in the film forming chamber 401, and the deposition chamber 401 and the activation chamber 4
07,408,409 was brought to a vacuum of 10 ^-5 Torr. The Al cylinder temperature was set at 290°C using an infrared lamp 403. Al cylinder 402,
It was lowered below the activation chamber 409. Next, the source gases shown in Table 1 are flowed into the activation chambers 407, 408, and 409, the internal pressure of the film forming chamber 401 is set to approximately 0.002 Torr, and the microwave power shown in Table 1 is applied to each activation chamber. did. After the microwave discharge state in the activation chamber stabilizes, the Al cylinder 402 is heated to 2.4
It was pulled up at a speed of mm/min. In this way, the blocking layer is approximately 3 μm thick and the photosensitive layer is approximately 20 μm thick.
A drum-shaped electrophotographic imaging member having a surface blocking layer of about 0.5 μm was prepared. When the electrophotographic properties of this electrophotographic image forming member were examined, sufficient properties for practical use were obtained. Example 3 In Example 1, the introduction position 213 of the precursor in the activation chamber 202 was changed, a photosensitive layer was deposited, and evaluation as a photoreceptor material for electrophotography was performed. As the active species raw material introduced into the activation chamber 202, H ₂ gas was used at a flow rate of 300 SCCM, and similarly, as the precursor raw material, SiF ₄ gas was used at a flow rate of 300 SCCM.
It was set to 300SCCM. The internal pressure of the film forming chamber 201 was set to 0.002 Torr by an exhaust valve 210. Activation chamber 2
A microwave of 300 W was applied to the chamber of 02, and the film was deposited for 1 hour and evaluated as a photoreceptor material for electrophotography. The results shown in Table 2 were obtained.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing a layer structure for explaining one embodiment of an electrophotographic imaging member produced using the method of the present invention. Figures 2 and 3
4 are schematic explanatory diagrams each showing an example of an apparatus for implementing the manufacturing method of the present invention. 201... Film formation chamber (A), 202... Activation chamber (B),
203, 204...Activation energy introduction wall and activated species raw material gas discharge wall, 205...Precursor raw material gas discharge pipe, 206...Microwave power source, 2
07...Al cylinder, 208...Heating heater, 209...Motor, 210...Exhaust valve, 211...Precursor raw material gas introduction pipe, 21
2...Active species raw material gas introduction pipe, 213...Distance between activation chamber outlet and precursor raw material gas discharge port, 3
01...Activation chamber (B), 302...Precursor raw material gas release pipe, 303...Microwave power source, 304
...Active species raw material gas introduction pipe, 305...Flow rate control valve, 306...Flow rate control valve, 307...
...Precursor raw material gas introduction pipe, 401... Film forming chamber
(A), 402... Al cylinder, 403... Infrared lamp, 404... Reflector, 405... Motor, 406... Rotating shaft, 407... Activation chamber (B),
408...Activation chamber (B), 409...Activation chamber (B),
410...Exhaust valve.

Claims (1)

[Claims] 1. A precursor used for forming a photoreceptive layer and an active species that chemically reacts with the precursor are introduced into a film forming space, and electrons arranged in the film forming space are A method for producing an electrophotographic photoreceptor in which a photoreceptive layer is formed on a photographic substrate, wherein the active species is transported through a first transport space that communicates downstream with the film forming space, and the precursor is Each of them is introduced into the film forming space through a second transport space having an opening to the first transport space and communicating with the film forming space, which is provided in the first transport space. A method for producing a featured electrophotographic photoreceptor. 2. The method of manufacturing an electrophotographic photoreceptor according to claim 1, wherein the activated species are generated in an activation space provided upstream of the first transport space. 3. The method of manufacturing an electrophotographic photoreceptor according to claim 1, wherein the first transportation space also serves as an activation space. 4. Claim 1, wherein the precursor is produced in a precursor space provided upstream of the second transport space.
The method for producing an electrophotographic photoreceptor as described in 2. 5. The method for manufacturing an electrophotographic photoreceptor according to claim 1, wherein the second transportation space also serves as a precursor formation space. 6. A photoreceptive layer is formed on an electrophotographic substrate placed in the film forming chamber by introducing a precursor used for forming the photoreceptive layer and an active species that chemically reacts with the precursor into a film forming chamber. An electrophotographic photoreceptor manufacturing apparatus comprising: a first transport path; an activation space provided upstream of the first transport path for generating the active species; a second transportation path having an opening opening to the first transportation path, and the precursor provided upstream of the opening of the second transportation path; a precursorization space; and the first
and a film forming chamber communicating with each of the second transportation path.