Electrophotographic photosensitive member process and apparatus for the preparation thereof

Abstract: An improved electrophotographic photosensitive member having a desired light receiving layer prepared by the use of a substance capable of contributing to form a deposited film and an electronically oxidizing agent in the absence of a plasma. A process and an apparatus for preparing the electrophotographic photosensitive member.

Description: This invention relates to an improved process for the deposition of an amorphous silicon film for use in an electrophotographic photosensitive member. There have been proposed a number of electrophotographic photosensitive members having a light receiving layer composed of a non-crystalline material containing silicon atoms as the main component, the so-called amorphous silicon (hereinafter referred to as "a-Si") disposed on a substrate. Also there have been proposed various methods for the preparation of such light receiving layer for the electrophotographic member using vacuum evaporation technique, heat chemical vapour deposition technique, plasma chemical vapour deposition technique, reactive sputtering technique, ion plating technique and light chemical vapour deposition technique. Among these methods, a method using a plasma vapour deposition technique (hereinafter referred to as "plasma CVD method") has been generally recognized as being the most preferred and is currently used to manufacture said light receiving layer. However, for any of the known light receiving layers, even if it is an acceptable one that is obtained by plasma CVD method and that exhibits almost satisfactory characteristics, there still remain problems unsolved in satisfying totally the points for its characteristics, particularly electric and optical characteristics, photoconductive characteristics, deterioration resistance upon repeating use and use-environmental characteristics, other points relating to its homogeneity, reproducibility and mass-productivity and further points relating to its lasting stability and durability. The reasons are largely due to the fact that the light receiving layer cannot be prepared easily by a simple layer deposition procedure but skill is required in the process operations in order to obtain a desirable light receiving layer while having due regard to the starting materials. For example, in the case of forming a film composed of an amorphous silicon material (hereinafter referred to as "a-Si") by a heat chemical vapor deposition technique (hereinafter referred to as "CVD method"), after the gaseous material containing silicon atoms has been diluted, appropriate impurities are introduced thereinto and the thermal decomposition of related materials is carried out at an elevated temperature between 500 and 650°C. Therefore, in order to obtain a desirable a-Si film by CVD method, precise process operation and control are required, and because of this, the apparatus in which the CVD method is practiced will be complicated and costly. However, even in that case, it is extremely difficult to obtain stably a desirable light receiving layer composed of an a-Si material, having an abundance of practically applicable characteristics, on an industrial scale. Now, although the plasma CVD method is widely used it is still accompanied with problems relating to process operations and to plant investment. Regarding the former problems, the operation conditions to be employed under the plasma CVD method are much more complicated than the known CVD method, and it is extremely difficult to generalize them. That is, there already exist a number of variations even in correlated parameters concerning the temperature of a substrate, the amount and the flow rate of gases to be introduced, the degree of pressure and the high frequency power for forming a layer, the electrode structure, the reaction chamber design, the flow rate of gases to be exhausted, and the plasma generation system. Besides said parameters, there also exist other kinds of parameters. Under these circumstances, in order to obtain a desirable deposited film product it is required to choose precise parameters from a great number of varied parameters. And sometimes serious problems occur. For instance, because the precisely chosen parameters are critical, plasma is apt to be in an unstable state which invites problems in film deposition. Also for the apparatus in which the process using the plasma CVD method is practiced, its structure will be complicated since the parameters to be employed are precisely chosen as above stated. Whenever the scale or the kind of the apparatus to be used is modified or changed, the apparatus must be so structured as to cope with the precisely chosen parameters. In this regard, even if a desirable deposited film should be fortuitously mass-produced, the film product becomes unavoidably costly because (1) a heavy investment is firstly necessitated to set up a particularly appropriate apparatus therefor ; (2) a number of process operation parameters even for such apparatus still exist and the relevant parameters must be precisely chosen from the existing various parameters for the mass-production of such film. In accordance with such precisely chosen parameters, the process must then be carefully practiced. Against this background, electrophotographic photosensitive members have become diversified. And there is an increased demand to provide stably a relatively inexpensive electrophotographic photosensitive member having a light receiving layer with a normal square measure or a large square measure composed of an a-Si material which has a relevant uniformity and many applicable characteristics and which is suited for the intended application. Consequently, there is an earnest desire to develop an appropriate method to meet satisfactorily the above demand. Likewise, there is a similar situation which exists with respect to other kinds of non-monocrystalline light receiving layers for electrophotographic photosensitive member, for example, those composed of an a-Si material containing at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms [hereinafter referred to as "a-Si(H,X)(O,C,N)"]. The present inventors have conducted extensive studies in order to solve the problems in the aforementioned known methods and in order to develop a new process for effectively and simply preparing an improved electrophotographic photosensitive member having a desirable light receiving layer composed of a non-crystalline semiconducting material, which has a wealth of practically applicable characteristics, without depending upon any known method and which meets the above-mentioned demands. As a result, the present inventors finally have found a process that enables one to efficiently and stably prepare said electrophotographic photosensitive member in simplified particular procedures as detailed below. According to the present invention there is provided a process for the deposition of an amorphous silicon film for use in an electrophotographic photosensitive member, which process comprises: providing in an evacuated chamber a rotatable substrate, said evacuated chamber having connected thereto a plurality of concentrically arranged gas transportion conduits, a central one of which conduits is offset from a nozzle entry to said evacuated chamber by a distance of between 1 and 5 cm, there being thus a mixing region (B') provided in a space between said central one of the conduits and said nozzle entry to said chamber; maintaining said substrate at a temperature between room temperature and 450°C; introducing into said mixing region (B'), via said gas supplying means, a gaseous first substance comprising a naturally gaseous or a gasified hydride or halogen substituted hydride of silicon, which substance is capable of supplying at least the silicon constituent of said film, but which gaseous first substance in its original energy state is substantially incapable of contributing to the formation of said film; introducing separately into said mixing region (B'), via said gas supplying means, a gaseous oxidising agent comprising a halogen gas, a gasified halogen, or a nascent halogen or any of air, oxygen, ozone, a gaseous nitrogen oxide, or a peroxide, and causing said agent to mix with said first substance, said agent having the property of being capable of oxidising said first substance at a temperature below that at which pyrolysis of said gaseous first substance would occur, the volume ratio of said gaseous first substance and said gaseous oxidising agent being in a range of 1:100 to 100:1; and causing the mixture produced by the mixing of said gaseous first substance and said gaseous oxidising agent to come into contact with said substrate, whilst rotating said substrate, and maintaining pressure in said chamber in a range of 0.13 to 1.3 x 10⁴Pa (0.001 to 100 Torr), thereby, in the absence of plasma discharge, resulting in a chemical reaction of said gaseous first substance and said gaseous oxidising agent, which reaction generates precursors including precursors in an excited state and which then results in the deposition of said film on said substrate. Advantageously the above defined process may be applied to the manufacture of the light receiving layer and/or other constituent layers of the electrophotographic photosensitive member. As is evident from the foregoing definition the film forming conditions are much simplified by comparison with the state of the art methods mentioned above. The process does not involve plasma discharge and damage from such discharge is thus entirely avoided. Good film characteristics can be achieved and can be maintained during the process. Film deposition rates can be much increased and the process is well suited to mass production. Also homogenous and uniformly thick deposited films can be prepared by the aforementioned process. In the accompanying drawings: Fig. 1(A) is a cross-sectional view of a first electrophotographic photosensitive member produced by a process according to this invention; Fig. 1(B) is a cross-sectional view of a second electrophotographic photosensitive member produced by a process according to this invention; Fig. 1(C) is a cross-sectional view of a third electrophotoelectric photosensitive member produced by a process according to this invention; Fig. 1(D) is a cross-sectional view of a fourth electrophotoelectric photosensitive member produced by a process according to this invention; Fig. 1(E) is a cross-sectional view of a fifth electrophotographic photosensitive member produced by a process according to this invention; Fig. 1(F) is a cross-sectional view of a sixth electrophotographic photosensitive member produced by a process according to this invention; Fig. 2(A) is a schematic cross-sectional view of apparatus for performing the process of this invention; Fig. 2(B) is a schematic longitudinal-sectional view of the apparatus shown in figure 2(A); Fig. 2(C) is a schematic longitudinal-sectional view of the gas transporting conduit assembly of the apparatus shown in figures 2(A) and 2(B); and Figure 3 is a schematic diagram of another apparatus for performing the process according to this invention. This invention will now be explained more specifically referring to the drawings. The description is not intended to limit the scope of the invention. Electrophotographic photosensitive members each produced by a process according to this invention are represented typically by those shown in Figure 1(A) through 1(F). In any of the above electrophotographic photosensitive members, the substrate may be either electroconductive or electrically insulative. Such electroconductive substrate can include, for example, metals such as NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, Ti Pt, and Pb, or the alloys thereof. Such electrically insulative substrate can include, for example, film or sheet of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide; glass, ceramics, and paper. It is preferred that the electrically insulative substrate is applied with electroconductive treatment to at least one of the surfaces thereof and disposed with a light receiving layer on the thus treated surface. In the case of glass, for instance, electroconductivity is applied by disposing, at the surface thereof, a thin film made of NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In₂O₂, SnO₃, ITO (In₂O₃ + SnO₂), etc. In the case of the synthetic resin film such as polycarbonate film, the electroconductivity is provided to the surface by disposing a thin film of metal such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Tl, and Pt by means of vacuum deposition, electron beam vapor deposition, sputtering, etc. or applying lamination with the metal to the surface. The substrate may be of any configuration such as cylindrical, belt-like or plate-like shape, which can be properly determined depending on the applications. For instance, it is desirably configurated into an endless belt or cylindrical form in the case of continuous high speed production. The thickness of the substrate is properly determined so that the light receiving layer as desired can be formed. In the case where flexibility is required for the electrophotographic photosensitive member, it can be made as thin as possible within a range capable of sufficiently providing the function as the substrate. However, the thickness is usually greater than 10 µm in view of the fabrication and handling or mechanical strength of the support. Figure 1(A): The electrophotographic photosensitive member comprises a single light receiving layer 102 disposed on a substrate 101. The single light receiving layer 102 is composed of an a-Si material, preferably, an a-Si material containing, in addition to silicon atoms, at least one kind selected from hydrogen atoms (H) and halogen atoms (X) [hereinafter referred to as "a-Si(H,X)"]. The halogen atom (X) contained in the light receiving layer 102 include, specifically, fluorine, chlorine, bromine and iodine, fluorine and chlorine being particularly preferred. The amount of the hydrogen atoms (H), the amount of the halogen atoms (X) or the sum of the amounts for the hydrogen atoms and the halogen atoms (H+X) contained in the light receiving layer 102 is usually from 1 to 40 atm % and, preferably, from 5 to 30 atm %. It is possible for the above light receiving layer 102 to further contain germanium atoms (Ge) and/or tin atoms (Sn). In the case where the above light receiving layer 102 is composed of an a-Si(H,X) material containing germanium atoms (Ge) and/or tin atoms (Sn) [hereinafter referred to as "a-Si(Ge,Sn)(H,X)"], there is provided an improvement in the absorption spectrum characteristics in the long wavelength region of the light receiving layer. That is, incorporating at least one kind selected from germanium atoms and tin atoms into the light receiving layer becomes to bring about a desired electrophotographic photosensitive member which is more sensitive to light of wavelengths broadly ranging from short wavelength to long wavelength covering visible light then quickly responsive to light. This effect becomes more significant when a semiconductor laser emitting ray is used as the light source. The amount of germanium atoms and/or tin atoms in the light receiving layer 102 should be properly determined so that the object of the invention is effectively achieved. It is usually 1 to 6 x 10⁵ atomic ppm, preferably 10 to 3 x 10⁵ atomic ppm, and more preferably 1 x 10² to 2 x 10⁵ atomic ppm. It is also possible for the above light receiving layer 102 to contain a substance for controlling the conductivity. As such substance, herein can include atoms belonging to the group III of the periodic table that provide p-type conductivity (hereinafter simply referred to as "group III atoms") or atoms belonging to the group V of the periodic table that provide n-type conductivity (hereinafter simply referred to as "group V atoms"). Specifically, the group III atoms can include B (boron), Al (aluminum), Ga (gallium), In (indium) and Tl (thallium), B and Ga being particularly preferred. The group V atoms can include, for example, P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth), P and Sb being particularly preferred. In the case where either the group III or the group V atoms are incorporated into the light receiving layer 102, there is provided an electrophotographic photosensitive member having a light receiving layer of which the type of conductivity and the conductivity are appropriately controlled. The amount of either the group III or the group V in the light receiving layer 102 in that case is preferably from 1 x 10⁻³ to 1 x 10³ atomic ppm, more preferably, from 5 x 10⁻² to 5 x 10² atomic ppm, and, most preferably , from 1 x 10⁻¹ to 5 x 10² atomic ppm. Figure 1(B) through Figure 1(F); In any of these cases, the light receiving layer is of a multi-layered structure and has a photosensitive layer 103 as one of the constituent layers. The photosensitive layer 103 may be the same as the light receiving layer 102 of the first embodiment as shown in Figure 1(A). That is, in the second to sixth members shown in Figure 1(B) through Figure 1(F), the photosensitive layer 103 is composed of an a-Si(H,X) material or an a-Si(Ga,Sn)(H,X) material, if necessary, containing either the group III or the group V atoms. Referring Figure 1(B), the electrophotographic photosensitive member comprises a substrate 101; a light receiving layer 102 constituted by a layer 104 containing a substance for controlling the conductivity; and a photosensitive layer 103. In this case, the layer 104 contains a relatively large amount of the substance for controlling the conductivity, namely, either the group III or the group V atoms and functions as a charge injection inhibition layer. That is, in the case of incorporating the group III or group V atoms in a uniformly distributed state to a portion of the layer region in contact with the support, or the atoms are contained such that the distribution density of the group III or group V atoms in the direction of the layer thickness is higher on the side adjacent to the support, the constituting layer containing such group III or group V atoms or the layer region containing the group III or group V atoms at high concentration function as a charge injection inhibition layer. That is, in the case of incorporating the group III atoms, movement of electrons injected from the side of the support into the photosensitive layer can effectively be inhibited upon applying the charging treatment of at positive polarity at the free surface of the photosensitive layer. While on the other hand, in the case of incorporation the group III atoms, movement of positive holes injected from the side of the support into the photosensitive layer can effectively be inhibited upon applying the charging treatment at negative polarity at the free surface of the layer. The content in this case is relatively great. Specifically, it is generally from 30 to 5 x 10⁴ atomic ppm, preferably from 50 to 1 x 10⁴ atomic ppm, and most suitably from 1 x 10² to 5 x 10³ atomic ppm. Then, for the charge injection inhibition layer to produce the intended effect, the thickness (T) of the photosensitive layer and the thickness (t) of the layer or layer region containing the group III or group V atoms adjacent to the support should be determined such that the relation t/T ≦ 0.4 is established. More preferably, the value for the relationship is less than 0.35 and, most suitably, less than 0.3. Further, the thickness (t) of the layer or layer region is generally 3 x 10⁻³ to 10 µm, preferably 4 x 10⁻³ to 8 µm, and, most suitably, 5 x 10⁻³ to 5 µm. The distribution state of the group III or group V atoms and the amount of the group III or group V atoms are, of course, combined properly as required. For instance, in the case of disposing the charge injection inhibition layer at the end of the photosensitive layer on the side of the support, a substance for controlling the conductivity of a polarity different from that of the substance for controlling the conductivity contained in the charge injection inhibition layer may be contained in the photosensitive layer other than the charge injection inhibition layer, or a substance for controlling the conductivity of the same polarity may be contained by an amount substantially smaller than that contained in the charge inhibition layer. Referring Figure 1(C), the electrophotographic photosensitive member comprises;a substrate 101; a light receiving layer 102 constituted by an intermediate layer 105 containing at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms;and a photosensitive layer 103. In this case the intermediate layer 105 is composed of an a-Si(H,X) material containing at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms [hereinafter referred to as "a-Si (O,C,N)(H,X)"]. This is effective in increasing the photosensitivity and dark resistance of the light receiving layer and in improving adhesion between the substrate and the light receiving layer. And, since the intermediate layer 105 is also effective in efficiently preventing inflow of photocarriers from the side of the substrate 101 into the photosensitive layer 103 and in promoting movement of the photocarriers, which are generated in the photosensitive layer 103 and moved toward the substrate 101, from the side of the photosensitive layer 103 toward the substrate 101, it functions as a barrier layer. The amount of at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms contained in the intermediate layer 105 is determined while considering inter relationships such as the performance at the interface in contact with the substrate, in addition to the performance required for the light receiving layer, and it is preferably from 0.001 to 50 atomic %, more preferably, from 0.002 to 40 atomic %, and, most preferably, from 0.003 to 30 atomic %. The thickness of the intermediate layer 105 is preferred to be less than 5 µm. Further, the intermediate layer 105 may be made to function as a charge injection inhibition layer by incorporating either the group III or the group V atoms thereinto. Referring Figure 1(D), the electrophotographic photosensitive member comprises the substrate 101 and a light receiving layer constituted by the photosensitive layer 103 and a surface layer 106 having a free surface. In this case, the surface layer 106 is composed of an a-Si(H,X) material containing at least one kind selected from oxygen atoms (O), carbon atoms (C) and nitrogen atoms (N) in a uniformly distributed state [hereinafter referred to as "a-Si(O,C,N)(H,X)"]. The surface layer 106 is disposed on the photosensitive layer 103 for improving moisture-proofness, performance for continuous repeating use, electrical voltage withstanding property, circumstantial resistant property and durability, and these attributes can be attained by incorporating at least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms in the amorphous material constituting the surface layer. At least one kind selected from oxygen atoms, carbon atoms and nitrogen atoms are contained in a uniformly distributed state in the surface layer 106, by which the foregoing various properties can be improved in accordance with the increase in the content of such atoms. However, if the content is excessive, the layer quality is reduced and electrical and mechanism properties are also degraded. In view of the above, the amount of such atoms is preferably from 0.001 to 90 atm %, more preferably, from 1 to 90 atm % and, most preferably, from 10 to 80 atm %. The surface layer 106 has to be formed with an utmost care so as to obtain the properties as desired. That is, the state of the substance comprising silicon atoms, oxygen atoms and, further, hydrogen atoms and/or halogen atoms as the constituent atoms is from crystalline to amorphous state, the electrical property of the layer may vary from the conductive, to semiconductivity and insulating property and, further, the photoelectronical property of the layer may also vary from photoconductive to non-photoconductive property depending on the content of each of the constituents atoms and other conditions of preparation. Accordingly, it is essential to select the content for each of the constituents atoms and the preparation conditions such that the surface layer 106 having desired properties depending on the purpose can be formed. For instance, in the case of disposing the surface layer 106 mainly for improving the electrical voltage withstanding property, the amorphous material constituting the surface layer 106 is formed such that it exhibits remarkable electrically insulating behaviors under the working conditions. Further, in the case of disposing the surface layer 106 mainly for improving the properties in the continuous repeating use or the circumstantial-resistant property, the amorphous layer constituting the surface layer 106 is formed such that the layer has a photosensitivity to some extent to the irradiated light, although the degree of the electrically insulating property is somewhat moderated. The thickness of the surface layer is also one of the important factors for effectively attaining the purpose of this invention and it is properly determined depending on the desired purposes. It is, however, also, necessary that the layer thickness is determined in view of relative different relationships in accordance with the amounts of the oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms and hydrogen atoms contained in the layer or the properties required for the surface layer. Further, it should be determined also in economical point of view such as productivity or mass productivity. In view of the above, the thickness of the surface layer 106 is preferably from 3 x 10⁻³ to 30 µ, more preferably, from 4 x 10⁻³ to 20 µ and, most preferably, from 5 x 10⁻³ to 10 µ. Referring Figure 1(E), the electrophotographic photosensitive member comprises;a substrate 101; a light receiving layer 102 constituted by the charge injection inhibition layer 104, a photosensitive layer 103; and a surface layer 106. Referring Figure 1(F), the electrophotographic photosensitive member comprises the substrate 101 and a light receiving layer 102 constituted by a first layer 107 containing at least one kind selected from germanium atoms (Ge) and tin atoms (Sn) and a second layer 108 containing neither germanium atoms nor tin atoms. That is, the first layer 107 is composed of an a-Si (Ge,Sn)(H,X) material and the second layer 108 is composed of an a-Si(H,X) material. The electrophotographic photosensitive member of the type as shown in Figure 1(F) is made to have excellent various properties by incorporating germanium atoms and/or tin atoms in the first sensitive layer 107. Particularly, it becomes more sensitive to light of wavelengths broadly ranging from short wavelength to long wavelength covering visible light and it also becomes quickly responsive to light. This effect becomes more significant when a semiconductor laser emitting ray is used as the light source. The formation of a relevant light receiving layer 102 as explained above on the substrate 101 to prepare the electrophotographic photosensitive member is carried out in accordance with the foregoing procedures in which the corresponding substance A and the oxidizing agent are appropriately selected and used. That is, in the case of forming a layer composed of a-Si(H,X) material, a gaseous or gasifiable silicon hydride (silane) such as SiH₄, Si₂H₆, Si₃H₈ and Si₄H₁₀ or a gaseous or gasifiable halogen-substituted silicon hydride (halogenated silane) such as SiH₃Cl, SiH₃F and SiH₃Br may be preferably used as the starting substance A. Also as the oxidizing agent in that case, a halogen gas such as F₂, Cl₂, Br₂ and I₂ or a nascent state halogen such as nascent state fluorine, chlorine and iodine may be preferably used. And among these substances, F₂ gas and Cl₂ gas are most preferred. In the case of forming a layer composed of a-Si (Ge,Sn)(H,X) material, a gaseous or gasifiable substance for introducing germanium atoms or a gaseous or gasifiable substance for introducing tin atoms is selectively used in addition to the above silane gas or halogenated silane gas. The substance for introducing germanium atoms can include GeH₄, Ge₂H₆, Ge₃H₈, Ge₄H₁₀ and Ge₅H₁₂. As the substance for introducing tin atoms, there are, for example, tin hydrides such as SnH₄. As the oxidizing agent, any of the foregoing oxidizing agents can be used. And Fe gas or Cl₂ gas can be most preferably used. In the case of forming a layer composed of a-Si(H,X) containing the group III or the group V atoms or the layer composed of a-Si(Ge,Sn)(H,X) containing the group III or the group V atoms, in addition to the above mentioned substance A to be used in the formation of the layer composed of a-Si(H,X) or the layer composed of a-Si(Ge,Sn)(H,X), a gaseous substance containing the group III or the group V atoms as the constituent element is selectively used. And as the oxidizing agent to be used in this case, the same substance as used in the above case is used. Specifically, usable as the gaseous substance for the group III atoms are, B₂H₆, B₄H₁₀, B₅H₉, B₆H₁₀, B₆H₁₂, Al(CH₃)₃, Al(C₂H₅)₃, Ga(CH₃)₃ and In(CH₃)₃. Among these compounds, B₂H₆ is most preferred. Usable as the gaseous substance for the group V atoms are, for example, PH₃, P₂H₄, AsH₃, SbH₃ and BiH₃. Among these compounds, PH₃ is most preferred. The gaseous substance either for the group III atoms or for the group V atoms is introduced into a film forming space solely or together with the gaseous substance A such as SiH₄ or Si₂H₆, chemically contacted with the separately introduced gaseous oxidizing agent therein. And the gaseous substance A and the gaseous substance either for the group III atoms or for the group V atoms are activated by the action of the oxidizing agent to generate plural kinds of precursors containing excited precursors. Further, in the case of forming layer composed of a-Si(O,C,N)(H,X), in addition to the foregoing gaseous silane such as SiH₄ or Si₂H₆ or the foregoing gaseous halogenated silane such as SiH₃Cl, SiH₃F or SiH₃Br to be used as the gaseous substance A in the case of forming the layer composed of a-Si(H,X), there is used a gaseous or gasifiable nitrogen compound such as nitorgen (N₂), ammonia (NH₃), hydrazine (H₂NNH₂), hydrogen azide (HN₃) and ammonium azide (NH₄N₃) or a carbon atom containing compound such as saturated hydrocarbons of 1 to 4 carbon atoms, ethylenic hydrocarbons of 2 to 4 carbon atoms and acetylenic hydrocarbons of 2 to 3 carbon atoms. Specifically, the saturated hydrocarbons can include methane (CH₄), ethane (C₂H₆), propane (C₃H₈), n-butane (n-C₄H₁₀) and pentane (C₅H₁₂), the ethylenic hydrocarbons can include ethylene (C₂H₄), propylene (C₃H₆), butene-1 (C₄H₈) butene-2 (C₄H₈), isobutylene (C₄H₈) and pentene (C₅H₁₀) and the acetylenic hydrocarbons can include acetylene (C₂H₂), methylacetylene (C₃H₄) and butine (C₄H₆). And as the gaseous oxidizing agent, there is used an oxygen containing gas such as air, oxygen (O₂) and ozone (O₃), a gaseous nitrogen oxide such as dinitrogen oxide (N₂O), dinitrogen trioxide (N₂O₃) and dinitrogen tetraoxide (N₂O₄), a peroxide such as hydrogen peroxide (H₂O₂), halogen gas such as F₂, Cl₂, Br₂ and I₂, or a nascent state halogen such as nascent state fluorine, chlorine and iodine. Further in addition, in the case of forming the layer composed of a-Si(O,C,N)(H,X) containing either the group III atoms or the group V atoms, in addition to those gaseous substances to be used as the gaseous substance A in the above case of forming the layer composed of a-Si(O,C,N)(H,X), there is used the gaseous substance either for the group III atoms or for the group V atoms such as B₂H₆ gas or PH₃ gas. As the gaseous oxidizing agent, the above mentioned oxygen containing gas, gaseous nitrogen compound, halogen gas can be optionally used. In this process the conditions upon forming the photosensitive layer and other layers, for example, the combination of the gaseous substance A with the gaseous oxidizing agent, their mixing ratios, the gas pressure upon mixing those substances in the film forming space, their gas flow rates, the internal pressure upon forming a layer on the substrate, the carrier gas flow rate, the temperature of the substrate and the flow type of each gaseous substance when introduced into the film forming space are important factors for obtaining an appropriate having desired characteristics and they are appropriately selected while considering the functions of the layer to be formed. Further, since these layer forming conditions are organically correlated and may be varied depending upon the kind and the amount of each of the atoms contained in the layer, the conditions are to be determined taking these relationships into consideration. The volume ratio of the starting substance A to the electronically oxidizing agent on the basis of the flow ratio is preferably 1/100 to 100/1, and more preferably, 1/50 to 50/1. As for the volume ratio of the gaseous substance for controlling the conductivity to the gaseous substance A on the basis of the flow ratio is preferably 1/10⁶ to 1/10, more preferably, 1/10⁵ to 1/20, and most preferably, 1/10⁵ to 1/50. The gas pressure in the film forming space when the gaseous substance A is mixed with the gaseous oxidizing agent is preferred to be high in order to facilitate their chemical contact. But it is necessary to be determined with due regard to their reactivities. Therefore, it is preferably 10⁻² to 10⁶Pa (1x10⁻⁷ to 10 atmospheric pressure), and more preferably,10⁻¹ to 3x10⁵ Pa (1x10⁻⁶ to 3 atmospheric pressure). The internal pressure in the film forming space, namely, the pressure of the inner space wherein the substrate is placed is appropriately determined with due regard to the excited precursors to be generated in the above inner space and to the conditions which let those precursors derived from the excited precursors to become effective in forming a deposited layer. The internal pressure in the film forming space in the case where the reaction region is open-connected to the film forming region can be adjusted with the use of a differential exhausting means or a large scale exhausting device while having due regard to the correlated conditions relating to the introducing pressure and the introducing flow rate for each of the gaseous substance A, the gaseous oxidizing agent and the gaseous substance for controlling the conductivity when they are introduced into the reaction region of the film forming space. In the case where the conductance of the connecting part between the reaction region and the film forming region is relatively small, the internal pressure in the film forming region can be adjusted by controlling the amount of the exhausting gas by operating an exhausting device being connected to the film forming region. Further in the case where the reaction region and the film forming region are united and they are not structurally separated, it is desirable to conduct the gas exhaustion with a differential gas exhausting means or with the use of a large scale gas exhausting device. As above mentioned, the internal pressure in the film forming space is determined while having a due regard on the correlative pressure conditions in introducing the gaseous substance A, the gaseous oxidizing agent and the substance for controlling the conductivity into the film forming space. However, in general, the internal pressure is preferably, 0.13 to 1.3 x 10⁴ Pa (0.001 to 100 Torr), more preferably 1.3 to 4.0x10³ Pa (0.01 to 30 Torr), and most preferably, 6.6 to 1.3x10³ Pa (0.05 to 10 Torr). As for the form of the gas flow into the film forming space for each of the foregoing substances, they are appropriately designed with due regard to the geometrical arrangement of the gas flow inlet, the substrate and the gas flow outlet so that the gaseous substance A, the gaseous oxidizing agent and the substance for controlling the conductivity can be effectively introduced into and homogeneously and well mixed in the predetermined region of the film forming space to generate desired precursors and to bring about the effective formation of a deposited film on the substrate. The temperature of the substrate upon forming a deposited film thereon is properly determined according to the kind of a gaseous substance to be employed and also to the kind of a deposited film to be formed. That is, in the case of forming a deposited film composed of an amorphous material, it is preferably room temperature to 450°C, more preferably, 50 to 450°C, and, most preferably, 70 to 350°C. The temperature in the film forming space is properly determined with due regard to the temperature of the substrate so that desired precursors are effectively generated, and those precursors as generated and other precursors derived from the former precursors are not changed into undesired things during the film forming process in the film forming space. Now, description will be hereunder made on an apparatus suitable for practicing the above process Referring to Figures 2(A) and 2(C), there is shown a film forming chamber 201 which has a film forming space C in which is placed a substrate holder 211 for a drum shaped substrate 210. The holder 211 has an electric heater 211' connected to a power source by lead wires (not shown). The film forming chamber 201 is provided with an exhaust pipe 213 which is connected through a main valve 214 (serving to break vacuum in the film forming chamber) to an exhaust device (not shown). Double conduit 204 has a gaseous substance A transporting conduit 205 horizontally installed at the middle and gaseous oxidizing agent transporting conduit 202 horizontally provided with a circumferential wall. The double conduit has a gaseous oxidizing agent transporting space B between the inner wall face of the conduit 202 and the outer wall face of the conduit 205. The conduit 205 is open at one end adjacent to mixing region B' being situated at the downstream side and connected to the film forming space A through nozzle means or orifice means 212. The holder 211 for the substrate 210 is suspended from the upper wall of the film forming chamber 201 through a rotary shaft 215 which is mechanically connected to a motor M so that the holder 211 can be rotated, raised or lowered by the action of a rotary shaft 215. The conduit 202 has a plural number of gas liberation holes 203 in the inner wall. The position of the opening 205' of the conduit 205 is situated about 1 to 5 cm distance from the nozzle means 212. Feeding pipe 206 of the gaseous substance A from a reservoir (not shown) is connected to the conduit 205 through valve means 206'. Feeding pipe 209 of carrier gas is connected to the pipe way of the feeding pipe 206. Feeding pipe 203 of the gaseous oxidizing agent is connected to the conduit 202 through valve means 207'. Referring to Figure 3, there is shown an alternative apparatus for practicing the process described. It is provided with three double conduits 302', 302" and 302'' each respectively of the same structure as the double conduit 204 shown in Figure 2(A) through Figure 2(C). Every double conduit is open at one end to film forming space B of film forming chamber 301 through an appropriate nozzle means (not shown) as in the apparatus shown in Figure 2(A) through Figure 2(C). Holder 310 for substrate 310' in the drum form is suspended from the upper wall of the film forming chamber 301 through rotary shaft 315 being mechanically connected to motor 312 so that the holder 310 can be rotated, lifted or descended by the action of the rotary shaft 315. The film forming chamber 301 is provided with exhaust pipe 313 being connected through main valve 314 serving to break vacuum in the film forming chamber to an exhaust device (not shown). In the film forming chamber 301, there are longitudinally install infrared lamp 403 for heating the substrate 310' and mirror 311' reflecting the infrared radiation toward the substrate 310'. The advantages of this invention are now described in more detail by reference to the following Examples, which are provided here for illustrative purposes only, and are not intended to limit the scope of this invention. Example 1 An electrophotographic photosensitive member having a charge injection inhibition layer, a photosensitive layer and a surface layer or a substrate of the type as shown in Figure 1(E) was prepared using the apparatus shown in Figure 2(A) through Figure 2(C). In this example, the position of the opening 205' of the conduit 205 is adjusted to be about 3 cm distance from the surface of the substrate 210. Analuminium cylinder for electrophotography was used as the substrate 210, and it was firmly located on the holder 211. The vacuum in the film forming chamber was brought to and maintained at about 1.3 x 10⁻³ Pa (10⁻⁵ Torr) by regulating the exhaust valve 214. Then the heater 211' was ignited to heat the cylinder and it was maintained at about 300°C. Concurrently, the motor 212 was started. Firstly, a charge injection inhibition layer was formed using F₂ gas as the gaseous oxidizing agent, SiH₄ gas as the gaseous substance A and B₂H₆ gas as the gaseous substance for controlling the conductivity. That is, after confirming the valve 207' on the feeding pipe 207 for the gaseous oxidizing agent was closed, SiH₄ gas (100 %) and a gas containing 3000 ppm of B₂H₆ in He gas (hereinafter referred to as "B₂H₆/He gas") were introduced into the film forming space C respectively at a flow rate of 100 SCCM and 100 SCCM. After the flow amount of the gases became stable, the vacuum in the film forming chamber 201 was brought to and maintained at about 1.1x10²Pa (0.8 Torr) by regulating the exhaust valve 214. Thereafter, F₂ gas was introduced into the film forming space C by opening the valve 207' at a flow rate of 15 SCCM. Wherein, there was observed a strong blue luminescence all over the part near the surface of the cylinder where the gases were mixed. After 1 hour, it was found that a charge injection inhibition layer composed of a-Si:H:F containing boron atoms was uniformly formed on the cylinder. Secondly, a photosensitive layer was formed using SiH₄ gas, He gas and F₂ gas. That is, the feeding of F₂ gas and the feeding of B₂H₆/He gas were stopped by closing the corresponding valves, and the feedings of SiH₄ gas and He gas were continued at a flow rate of 200 SCCM and 100 SCCM respectively. After the flow amount of the gases became stable, the vacuum in the film forming chamber 201 was brought to and maintained at 1.1x10²Pa (0.8 Torr) by regulating the exhaust valve 214. Thereafter, F₂ gas was introduced into the film forming space C at a flow rate of 30 SCCM by opening the valve 207'. After 4.5 hours, it was found that a photosensitive layer composed of a-Si:H:F of 20 µm in thickness was uniformly formed on the previous charge injection inhibition layer. Finally, after the valve 207' was closed to stop the feeding of F₂ gas, SiH₄ gas, He gas and CH₄ gas were together introduced into the film forming space C respectively at a flow rate of 50 SCCM, 100 SCCM and 300 SCCM. After the flow amount of the gases became stable, the vacuum in the film forming chamber 201 was brought to and maintained at 1.1 x 10² Pa (0.8 Torr) by regulating the exhaust valve 214. Then, F₂ gas was introduced into the film forming space C. After 30 minutes, it was found that a surface layer film composed of a-SiC:H:F of about 500 nm (5000 Å) in thickness was uniformly formed on the above photosensitive layer. The feedings of all the gases were terminated by closing the corresponding valves, the heater was switched off, and the vacuum atmosphere in the film forming chamber was released to atmospheric pressure by opening the exhaust valve 214. After the cylinder 210 had cooled to room temperature, it was taken out from the film forming chamber 201. When observing the thus obtained electrophotographic photosensitive member, it was found that the member had a wealth of practically applicable electrophotographic characteristics. Also when examining the thickness and uniformity of the light receiving layer formed on the aluminium cylinder, it was found that the layer was of uniform thickness and of uniform homogeneity. Example 2 An electrophotographic photosensitive member having a charge injection inhibition layer, a photosensitive layer and a surface layer on a substrate of the type as shown in Figure 1(E) was prepared using the apparatus shown in Figure 3. An aluminium cylinder for electrophotography as the substrate 310' was firmly located on the holder 310. Then, the vacuum in the film forming chamber 301 was brought to and maintained at about 1.3x10⁻³Pa (10⁻⁵ Torr) by regulating the exhaust valve 314. Concurrently, the infrared lamp 403 was switched on to uniformly heat the cylinder to 290°C and it was maintained at that temperature. The position of the holder 402 was changed so as to adjust the top level of the cylinder to be situated under the opening of the double conduit 302''' , then the gaseous substance A and He gas were respectively introduced into the film forming space C of the film forming chamber 301 through the double conduits 302', 302'' and 302''' under the conditions shown in Table 1. After the flow amount of each gas became stable, the vacuum in the film forming chamber 301 was brought to and maintained at at about 1.1x10²Pa (o.8 Torr) by regulating the exhaust valve 314. Thereafter, F₂ gas as the gaseous oxidizing agent was introduced into the film forming space C through the double conduits 302', 302'' and 302''' under the conditions shown in Table 1. Wherein, there was observed a strong blue luminescence in the region ranging from the openings of the double conduits to the surface of the cylinder. While maintaining the above state, the cylinder was lifted at a speed of 1.7x10⁻³ cm/sec (1.0 mm/minute) while being rotated by the action of the rotary shaft 315. The film forming rate for the corresponding layer was as shown in Table 1. In this way, there was formed firstly a charge injection inhibition layer composed of a-Si:H:F containing boron atoms of about 2 µm in thickness, secondly a photosensitive layer composed of a-Si:H:F of about 20 µm in thickness and finally a surface layer composed of a-SiC:H:F of about 0.5 µm in thickness on the cylinder. The feedings of all the gases were terminated by closing the corresponding valves, the infrared lamp was switched off, and the vacuum atmosphere in the film forming chamber was released to atmospheric pressure by opening the exhaust valve 314. After the cylinder had cooled to room temperature, it was taken out from the film forming chamber 301. When observing the thus obtained electrophotographic photosensitive member, it was found that the member had a wealth of practically applicable electrophotographic characteristics. Also when examining the thickness and uniformity of the light receiving layer formed on the aluminum cylinder, it was found that the layer was of uniform thickness and of uniform homogeneity. Gas introducing conduit Gaseous substance A (SCCM) Gaseous oxidizing agent (SCCM) Carrier gas (SCCM) Film forming rate nm/s(Å/sec) 302' SiH₄=100 F₂ = 20 He=100 0.025 (0.25) CH₄ =300 302'' SiH₄=900 F₂ = 90 He=800 1.0 (10) 302''' SiH₄=300 F₂ = 30 He=150 0.1 (1) B₂H₆/He(1500 ppm) =100 Example 3 A light receiving layer was formed on an aluminium cylinder in the same manner as in Example 1 with the film forming conditions shown in Table 2. When observing the thus obtained electrophotographic photosensitive member, it was found that the member has a wealth of practically applicable many electrophotographic characteristics. And when examining the thickness and uniformity of the light receiving layer formed on the aluminum cylinder, it was found that the layer is of uniform thickness and of uniform homogeneity. Constituent Layer Gaseous substance A (SCCM) Gaseous oxidizing agent(SCCM) Carrier Gas (He) (SCCM) Layer thickness Charge injection inhibition layer SiH₄ = 300 O₂= 30 150 300 nm (3000Å) B₂H₆/He(1500ppm) = 100 Photosensitive layer SiH₄ = 900 O₂=100 450 10µm Surface layer SiH₄ = 100 O₂= 10 50 100 nm (1000Å) CH₄ = 300 Temperature of substrate : 250°C The vacuum in the film forming chamber : 1.3x10²Pa (1.0 Torr) Example 4 A light receiving layer was formed on an aluminium cylinder in the same manner as in Example 2 with the film forming conditions shown in Table 3. When observing the thus obtained electrophotographic photosensitive member, it was found that the member has a wealth of practically applicable many electrophotographic characteristics. And when examining the thickness and uniformity of the light receiving layer formed on the aluminum cylinder, it was found that the layer is of uniform thickness and of uniform homogeneity. Gas introducing conduit Gaseous substance A (SCCM) Gaseous oxidizing agent (SCCM) Carrier gas (He gas) (SCCM) Film forming rate m/s(Å/sec) 302' SiH₄ = 200 O₂= 50 50 0.02 (0.2) CH₄ = 400 302'' SiH₄ = 1500 O₂=300 300 0.2 (2) 302''' SiH₄ = 600 O₂= 60 60 0.005 (0.05) B₂H₆/He(1500ppm) = 200 Temperature of substrate : 250°C The vacuum in the film forming chamber : 1.3x10² Pa (1.0 Torr)

Claims: A process for the deposition of an amorphous silicon film for use in an electrophotographic photosensitive member, which process comprises: providing in an evacuated chamber (201, 301) a rotatable substrate (210, 310), said evacuated chamber having connected thereto a plurality of concentrically arranged gas transportion conduits (204, 205), a central one (205) of which conduits (204, 205) is offset from a nozzle entry to said evacuated chamber (201, 301) by a distance of between 1 and 5 cm, there being thus a mixing region (B') provided in a space between said central one (205) of the conduits (204, 205) and said nozzle entry to said chamber (201,301); maintaining said substrate at a temperature between room temperature and 450°C; introducing into said mixing region (B'), via said gas supplying means (204, 205), a gaseous first substance comprising a naturally gaseous or a gasified hydride or halogen substituted hydride of silicon, which substance is capable of supplying at least the silicon constituent of said film, but which gaseous first substance in its original energy state is substantially incapable of contributing to the formation of said film; introducing separately into said mixing region (B'), via said gas supplying means (204, 205), a gaseous oxidising agent comprising a halogen gas, a gasified halogen, or a nascent halogen or any of air, oxygen, ozone, a gaseous nitrogen oxide, or a peroxide, and causing said agent to mix with said first substance, said agent having the property of being capable of oxidising said first substance at a temperature below that at which pyrolysis of said gaseous first substance would occur, the volume ratio of said gaseous first substance and said gaseous oxidising agent being in a range of 1:100 to 100:1; and causing the mixture produced by the mixing of said gaseous first substance and said gaseous oxidising agent to come into contact with said substrate (210, 310), whilst rotating said substrate (210, 310), and maintaining pressure in said chamber (201, 301) in a range of 0.13 to 1.3 x 10⁴Pa (0.001 to 100 Torr), thereby, in the absence of plasma discharge, resulting in a chemical reaction of said gaseous first substance and said gaseous oxidising agent, which reaction generates precursors including precursors in an excited state and which then results in the deposition of said film on said substrate (210, 310). A process as claimed in claim 1 wherein a naturally gaseous or gasified second substance containing atoms of germanium and/or tin is used in addition to said first substance. A process as claimed in claim 2 wherein said second substance comprises a hydride of germanium or tin. A process as claimed in any of claims 1-3 wherein a naturally gaseous or gasified third substance containing atoms of a group III element, or alternatively containing atoms of a group V element, is used in addition to said first substance, this third substance being introduced either separately from or with said first substance. A process as claimed in claim 4 wherein said third substance comprises a boron halide or an alkyl compound of aluminium, gallium or indium. A process as claimed in claim 4 wherein said third substance comprises a halide of phosphorus, arsenic, antimony or bismuth. A process as claimed in either claim 1 or claim 4 when depending directly from claim 1, wherein a naturally gaseous or gasified fourth substance containing nitrogen or carbon is used in addition to said first substance. A process as claimed in claim 7 wherein said fourth substance containing nitrogen comprises nitrogen, ammonia, hydrazine, hydrogen azide or ammonium azide. A process as claimed in claim 7 wherein said fourth substance containing carbon comprises a saturated hydrocarbon of 1 to 4 carbon atoms, an ethylenic hydrocarbon of 2 to 4 carbon atoms or an acetylenic hydrocarbon of 2 to 3 carbon atoms. A process for the deposition of successive amorphous silicon films of an electrophotographic photosensitive member (101,104,103 of fig.1(B)), which process comprises performing a process as claimed in any of claims 4-6 to deposit a charge injection inhibition layer (104); and thereafter performing a process as claimed in any of claims 1-6 to deposit a photosensitive layer (103) on said charge injection inhibition layer (104). A process for the deposition of successive amorphous silicon films of an electrophotographic photosensitive member (101,105,103 of fig. 1(C)), which process comprises: performing a process as claimed in any of claims 1, 7-9 to deposit an intermediate or barrier layer (105); and thereafter performing a process as claimed in any of claims 1-6 to deposit a photosensitive layer (103) on said intermediate or barrier layer (105). A process for the deposition of successive amorphous silicon films of an electrophotographic photosensitive member (101,103,106 of fig. 1(D); 101,104,103,106 of fig. 1(E)); which process comprises: either performing a process as claimed in any of claims 1-6 to deposit a photosensitive layer (103); or performing a process as claimed in claim 10 to deposit a charge injection inhibition layer (104), and to deposit a photosensitive layer (103) on said charge injection inhibition layer (104); and thereafter performing a process as claimed in any of claims 1, 7-9 to deposit a surface protection layer (106) on said photosensitive layer (103). A process as claimed in claim 12 wherein respective adjacent pluralities of concentrically arranged conduits (302',302'',302''') are used for introducing said substances and said agent for respective ones of said deposited layers (104,103,106). A process for the deposition of successive amorphous silicon films of an electrophotographic photosensitive member (101,107,108 of fig.1(F)), which process comprises: performing a process as claimed in either of claims 2 or 3 to deposit a first photosensitive layer (107) containing germanium and/or tin; and thereafter performing a process as claimed in claim 1 to deposit a second photosensitive layer (108) containing neither germanium nor tin.

Inventors: HANNA JUNICHI, HIROOKA MASAAKI, ISHIHARA SHUNICHI, SHIMIZU ISAMU, HANNA, JUNICHI, HIROOKA, MASAAKI, ISHIHARA, SHUNICHI, SHIMIZU, ISAMU
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1986
Main classification: G03G5
IPC codes: G03G5, C23C16