IIIUS005284730A United States Patent (19) 11) Patent Number: 5,284,730 Takei et al. (45) Date of Patent: Feb. 8, 1994

(54) ELECTROPHOTOGRAPHIC 56) References Cited LIGHT-RECEIVING MEMBER U.S. PATENT DOCUMENTS (75) Inventors: Tetsuya Takei, Nagahama; Shigeru 4,225,222 9/1980 Kempter ...... 355/3 DR Shirai, Hikone; Hirokazu Ohtoshi, 4,265,991 5/1981 Hirai et al...... 430/64 Nagahama; Ryuji Okamura, Shiga; 4,483,911 11/1984 Ogawa et al. . ... 430/65 Yasuyoshi Takai, Nagahama; 4,539,283 9/1985 Shirai et al. ... . 430/61

4,775,606 10/1988 Shirai ...... 430/67 Hiroyuki Katagiri, Shiga, all of Japan 4,792,509 12/1988 Shirai et al. . ... 430/64 4,824,749 4/1989 Shirai et al...... 430/66 (73) Assignee: Canon Kabushiki Kaisha, Tokyo, Japan FOREIGN PATENT DOCUMENTS 2746967 4/1979 Fed. Rep. of Germany . 21 Appl. No.: 925,617 2855718 6/1979 Fed. Rep. of Germany. 57-11556 1/1982 Japan . 60-67951 4/1984 Japan . 22) Filed: Aug. 6, 1992 62-16861 7/1987 Japan. Primary Examiner-John Goodrow Related U.S. Application Data Attorney, Agent, or Firm-Fitzpatrick, Cella, Harper & (63) Continuation-in-part of Ser. No. 780,780, Oct. 23, 1991. Scinto (30) Foreign Application Priority Data 57 ABSTRACT Oct. 24, 1990 (JP) Japan ...... 2-287564 An electrophotographic light-receiving member has a Oct. 24, 1990 (JP Japan ...... 2-2875.65 surface layer of a non-single crystal material (SixCO2)- Mar. 29, 1991 (JP) Japan ...... 3-89316 HF (wherein 0.1 SxS 0.4, 0.4sys 0.7, 0.05Szs 0.2, Aug. 30, 1991 JP Japan ...... 3-220385 X-y-Z = 1, 0.299 sts 0.589, 0.41 Sus 0.7, Aug. 30, 1991 (JP) Japan ...... 3-220386 0.001 Sv S0.1 and t-u-v = 1), in which the ratio of atoms bonded to carbon atoms in the surface Sep. 20, 1991 JP Japan ...... 3-24.1751 layer is at least 50% of the total number of silicon atoms, 51) Int. Cl...... G03G 5/14 and the ratio of silicon atoms bonded to oxygen atoms is 52 U.S.C...... 430/66 10 to 30 atomic 9% of the total number of silicon atoms. 58 Field of Search ...... 430/58, 59, 66, 67, 430/84, 95 7 Claims, 6 Drawing Sheets U.S. Patent 5,284,730

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O or o N. vo LAn s r. N. v. O re ('qJD) ALISN3LN1 5,284,730 1. 2 vironmental conditions for a longer time, without being ELECTROPHOTOGRAPHIC LIGHT-RECEIVING subjected to maintenance by a service man. MEMBER In this situation, the fact is that conventional electro photographic light-receiving members have room for This is a continuation-in-part of application Ser. No. improvement. 07/780,780, filed Oct. 23, 1991. Particularly, the repeated use of the members at a BACKGROUND OF THE INVENTION high speed for a long time under high humidity some times causes the phenomenon that the fine lines on the Field of the Invention image formed are blurred (image flowing), and in the The present invention relates to an electrophoto 10 extreme case, the characters of the image cannot be graphic light-receiving member having sensitivity to read. In addition, once an electrophotographic light electromagnetic waves such as light (including ultravio receiving member in an electrophotographic apparatus let rays, visible rays, infrared rays, X-rays, y-rays and has produced the above phenomenon, it will continue to the like). produce image flowing even if it is returned to environ 15 mental conditions under relatively low humidity which Description of the Related Art previously produced no image flowing. In a conven In the field of image formation, photoconductive tional method of preventing such image flowing caused materials used for forming a light-receiving layer in an under high humidity, a drum is heated for decreasing electrophotographic light-receiving member are re the relative humidity on the surface of the drum. How quired to have properties such as high sensitivity, high 20 ever, this method requires heating of the surface of the SN ratio, absorption spectral properties which conform drum to an extremely high temperature. Thus, the cost with the spectral properties of the electromagnetic of the apparatus and the electricity consumption are wave applied thereto, high photoresponsibility, desired increased, and the toner used sometimes adheres to the dark resistance values, harmlessness to human bodies during use and the like. 25 surface of the drum depending upon the set tempera A photoconductive material found to have such ex ture. cellent properties is amorphous silicon (referred to as In addition, when a light-receiving member having a "A-Si or a-Si" hereinafter). For example, Germany hard surface with high durability is repeatedly used for Patent Laid-Open Nos. 2746967 and 2855718 and Japa a long time, as described above, the toner used some nese Patent Laid-Open No. 54-86341 disclose the appli 30 times adheres to the drum (filming), producing nonuni cation of A-Sito an electrophotographic light-receiving formity in density and blurs on the image formed. member. SUMMARY OF THE INVENTION Japanese Patent Laid-Open No. 57-11556 discloses a technique in which a surface barrier layer made of a It is an object of the present invention to solve the non-photoconductive amorphous material containing 35 above-described problems of a conventional electro silicon and carbon atoms is provided on a photoconduc photographic light-receiving member having a light tive layer made of a silicon-based amorphous material receiving layer made of A-Si. for the purpose of attempting to improve the electrical, Namely, it is a main object of the present invention to optical and photoconductive properties, such as the provide an electrophotographic light-receiving member dark resistance value, photosensitivity, photoresponsi having a light-receiving layer made of a silicon-based bility and the like, of a photoconductive member having non-single crystal material which has electrical, optical a photoconductive layer comprising an A-Sideposited and photoconductive properties which are substantially film, the working environmental properties thereof constantly stable without depending upon the working such as humidity resistance and the like, and the time environment, which has excellent optical fatigue resis stability. 45 tance, excellent durability without any deterioration In addition, Patent Application No. 62-168161 dis during repeated use, and excellent moisture resistance, closes a technique which uses as a material for a surface which shows substantially no residual potential and layer a material consisting of an amorphous substance which produces substantially no filming of toner after containing as components silicon atoms, carbon atoms repeated use. and 41 to 70 atomic 9% of hydrogen atoms. 50 According to a first aspect of the present invention, Further, Patent Application No. 60-67951 discloses a an electrophotographic light-receiving member com technique for a photosensitive material in which a light prises a substrate and a light-receiving layer formed on transmitting insulating overcoat layer containing amor the substrate. The light-receiving layer has a surface phous silicon, carbon, oxygen and is laminated layer or a surface-side region formed of a non-single on the photosensitive material. 55 crystal material comprising silicon, carbon and hydro The above techniques permit improvement in the gen atoms, where the ratio of silicon atoms each having electrical, optical and photoconductive properties of an at least one bond to a carbon aton in the surface layer electrophotographic light-receiving member, the work or surface-side region is at least 50% of the total number ing environmental properties and durability thereof, of silicon atoms in the surface layer or surface-side and the quality of the image formed. region. On the other hand, as the copying speed, the printing According to another aspect of the present invention, speed (image forming speed) and durability of an elec an electrophotographic light-receiving member com trophotographic apparatus are rapidly increased, the prises a non-single crystal layer comprising at least frequency of maintenance must be decreased for de silicon, carbon, oxygen, hydrogen and fluorine atoms creasing the service cost by improving the reliability of 65 on an outermost surface layer, wherein the ratio of each of the parts of the apparatus. In these circum silicon atoms bonded to carbon atoms in the non-single stances, an electrophotographic light-receiving member crystal layer is 50 to 100 atomic % of the total number can be continuously repeatedly used under various en of silicon atoms therein, the ratio of silicon atoms 5,284,730 3 4. bonded to oxygen atoms in the non-single crystal layer ratio of bonds between silicon and carbon atoms and the is 10 to 30 atomic % of the total number of silicon atoms ratio of bonds between silicon and oxygen atoms to therein, and the non-single crystal layer is substantially values within desired ranges. composed of a non-single crystal (SiCO).H.F, Particularly, the ratio of silicon atoms each having at wherein 0.1 SxS 0.4, 0.4sys 0.7, 0.05szs0.2, least one bond to a carbon atom to the total number of x+y+z= 1, 03sts 0.59, 0.41sus 0.7, 0.001 s vs 0.1 silicon atoms in the surface layer or the surface region is and t-i-u--v= 1. set to be at least 50 atomic 26, and the ratio of silicon According to yet another aspect of the present inven atoms each having at least one bond to an oxygen atom tion, an electrophotographic light-receiving member to the total number of silicon atoms therein is within the comprises a non-single crystal layer comprising at least 10 range of 10 to 30 atomic %. silicon, carbon, oxygen, hydrogen and fluorine atoms The electrophotographic light-receiving member of on an outermost surface, wherein the ratio of silicon the present invention comprises a substrate and a light atoms bonded to carbon atoms in the non-single crystal receiving layer having a photoconductive layer region layer is 50 to 100 atomic 76 of the total number of silicon which is made of a silicon-based non-single crystal ma atoms, the ratio of silicon atoms bonded to oxygen 15 terial containing as a component at least one of hydro atoms is 10 to 30 atomic 9% of the total number of silicon gen and atoms and which exhibits photocon atoms, the ratio of carbon atoms bonded to oxygen ductivity, and a surface layer region which is made of a atoms is 10 to 30 atomic 2% of the total number of car non-single crystal material containing as components bon atoms, and the non-single crystal layer is substan silicon, carbon, oxygen, hydrogen and fluorine atoms, tially composed of a non-single crystal having the for 20 both regions being formed on the substrate, wherein the mula (SiCO).H.F, wherein 0.1 sxs 0.4, 0.4sy ratio of silicon atoms each having at least one bond to a s0.7, 0.05szs 0.2, x-y--z= 1, 0.3sts 0.59, carbon atom in the surface layer region is at least 50% 0.41 SuS 0.7, 0.001 Sv S0.1 and t- u + v = 1. of the total number of silicon atoms in the surface layer region. BRIEF DESCRIPTION OF THE DRAWINGS 25 In another feature of the invention, the electrophoto FIG. 1 shows a schematic drawing of a layer struc graphic light-receiving member has an outermost sur ture for explaining the layer structure of an electropho face comprising a non-single crystal layer which con tographic light-receiving member according to the tains at least silicon, carbon, oxygen, fluorine and hy present invention; drogen atoms, wherein the ratio of silicon atoms bonded FIGS. 2(A), (B) and (C) are explanatory views re 30 to carbon atoms in the non-single crystal layer is 50 to spectively showing examples of the uneven shape of the 100 atomic 9% of the total number of silicon atoms, the surface of a substrate; ratio of silicon atoms bonded to oxygen atoms is 10 to FIG. 3 is an explanatory view showing another exam 30 atomic 9% of the total number of silicon atoms, and ple of the uneven shape of the surface of a substrate; the non-single crystal layer is made of a non-single crys FIG. 4 is a schematic drawing showing a method of 35 tal (SiCO).H.F (wherein 0.1sxs 0.4, 0.4sys 0.7, forming the example of the uneven shape shown in 0.05szs 0.2, x+y+z= 1, 0.3sts 0.59, 0.41sus 0.7, FIG. 3; 0.001 Sv S0.1 and t-i-u-- v = 1). FIG. 5 is an explanatory view showing a further In a further feature of the invention, the electropho example of the uneven shape of a substrate; tographic light-receiving member has an outermost FIG. 6 is a schematic drawing showing an example of 40 surface comprising a non-single crystal layer which apparatuses for producing a drum by microwave dis contains at least silicon, carbon, oxygen, fluorine and charge for forming a light-receiving layer of an electro hydrogen atoms, wherein the ratio of silicon atoms photographic light-receiving member according to the bonded to carbon atoms in the non-single crystal layer is present invention; 50 to 100 atomic % of the total number of silicon atoms, FIG. 7 is a plan view of the production apparatus 45 the ratio of silicon atoms bonded to oxygen atoms is 10 shown in FIG. 6; and to 30 atomic % of the total number of silicon atoms, the FIGS. 8 and 9 are drawings of an example of spectra ratio of carbon atoms bonded to oxygen atoms is 10 to obtained by ESCA (Electron Spectroscopy for Chemi 30 atomic % of the total number of carbon atoms, and cal Analysis) of the surface of an electrophotographic the non-single crystal layer is made of a non-single crys light-receiving member according to the present inven 50 tal expressed by the formula (SiC.O.).H.F, (wherein tion. 0.1 sxs 0.4, 0.4sys 0.7, 0.05 SzS 0.2, x-y-z = 1, 0.3sts 0.59, 0.41sus 0.7, 0.001 s vs 0.1 and DESCRIPTION OF THE PREFERRED t-u-v= 1). EMBODIMENT OF THE INVENTION The electrophotographic light-receiving member of In an electrophotographic light-receiving member 55 the present invention designed so as to have the above according to the present invention which enables the layer structure is capable of solving all the above-men above-described problems to be solved and the objects tioned problems and shows extremely excellent electri to be achieved, a ratio of bonds between silicon and cal, optical and photoconductive properties, durability carbon atoms in the region on the external surface side and working environmental properties. or the surface layer of the electrophotographic light The present invention can provide an electrophoto receiving member is set to a value within a desired graphic light-receiving member showing an excellent region. effect for preventing the occurrence of filming. Particularly, the ratio of silicon atoms each having at The electrophotographic light-receiving member of least one bond to a carbon atom to the total number of the present invention is described below. silicon atoms in the surface layer or the surface region is 65 As a result of energetic investigation conducted by set to be at least 50 atomic 9%. the inventors having attention to the point that the It is also desirable to more sufficiently solve the above problems can be solved by improving the surface above-described filming problem to respectively set the layer, the inventors found that the object is achieved by 5,284,730 5 6 specifying a method of bonding silicon atoms in the As described above, a surface layer or surface region surface layer. (generically named "surface layer” hereinafter) of a The inventors believe that an electrophotographic light-receiving member is generally made of a non-sin apparatus which employs a conventional electrophoto gle crystal material containing as components silicon, graphic light-receiving member produces image flow carbon and hydrogen atoms for the purpose of improv ing under a high-humidity environment due to the two ing the electrical, optical and photoconductive proper following phenomena which are considered as impor ties, working environmental properties, durability and tant mechanisms for image flowing: the quality of the image formed. (1) The phenomenon that hygroscopic substances The amount of carbon atoms contained in such a such as oxides like NOx are generated during co 10 surface layer is 1 x 10-3 to 90 atomic 9%, preferably 10 rona discharge by a charger, causing paper powder to 80 atomic 9%, relative to 100% of the total of silicon produced from transfer paper and the like to ad and carbon atoms. When the surface layer is formed here to the surface of the light-receiving member irrespective of the state of bonding between silicon and absorb water at high humidity. The resistance atoms and carbon atoms, the silicon and carbon atoms is therefore decreased, and image flowing thus 15 are not uniformly distributed, thereby producing a state OCCS. wherein portion with a high content of silicon atoms (2) The phenomenon that the reaction to the material and portions with a high content of carbon atoms are of the surface of the light-receiving member with mixed. oxygen contained in water and air due to corona The number of silicon atoms each having at least one energy causes a decrease in resistance, or an oxide 20 bond to a carbon atom is thus smaller than the value which is decreased in resistance by absorption of estimated from the above composition. water is produced, thereby causing image flowing. On the other hand, the inventors found that phenom Most of the substances adhered due to the phenome enon (2) is generated under corona discharge by bond non (1) can be removed by rubbing the light-receiving ing of oxygen with the dangling bonds of the silicon member with a toner, an abrasive contained in the 25 atoms which are present in the surface layer initially or toner, a blade or the like during the electrophoto which are produced by breakage of Si-H and Si-Si graphic process. If the adhered substances cannot be bonds, caused by corona energy. As a result of ESCA sufficiently removed, the light-receiving member is analysis of the surface of a light-receiving member separated from the electrophotographic apparatus by a which is produced irrespective of the bonding between service man so that the substance can be completely or 30 silicon and carbon atoms and which produces the phe substantially completely (to an extent which has no or nomenon (2), it was confirmed that about 10 to 30% of substantially no effect on the formation of an image) silicon atoms are joined to oxygen atoms. If the state of cleaned by wiping the surface of the member with wa bonding between the silicon and oxygen atoms is ex ter, an organic solvent or the like. pressed by SiO2, z is 1.0 to 1.5. It is also effective as a measure against the image 35 However, results of many experiments showed that if flowing caused by the phenomenon (1) to decrease the a silicon atom has at least one bond to a carbon atom, relative humidity of the surface by heating the light the above-described oxidation is not easily produced. In receiving member. this case, even if the oxidation is produced, the effect on However, the image flowing cased by the mechanism the electrophotographic properties is decreased. When described in the phenomenon (2) can hardly be re a light-receiving member is produced in sufficient con moved by rubbing the light-receiving member with a sideration of the ratio of bonding between silicon and toner, an abrasive contained in the toner, a blade or the carbon atoms, image flowing and the like are effectively like, or wiping the surface the light-receiving member removed. with water, an organic solvent or the like by a service It is only slightly effective to simply increase the flow 2. 45 rate of gas containing carbon atoms in the raw materials The method of decreasing the relative humidity of gases for the purpose of increasing the probability of the surface of the light-receiving member by heating it bonding between silicon and carbon atoms. As de is only slightly effective as a measure against the image scribed above, this is because silicon and carbon atoms flowing caused by phenomenon (2). If the light-receiv are not uniformly distributed in a deposited film. It is ing member is heated to a high temperature, the method 50 therefore difficult to increase the ratio of silicon atoms has an effect. each having at least one bond to a carbon atom to 30% In addition, the phenomenon (2) frequently causes or more of the total silicon atoms contained in the sur problems other than the image flowing, e.g., a decrease face layer by simply increasing the flow rate of the gas in sensitivity, an increase in residual potential and the containing carbon atoms. In addition, when the amount like. 55 of carbon atoms is increased, other properties such as Previously, although the above two phenomena are the mechanical strength required for an electrophoto not clearly separately considered, since, in fact, the graphic light-receiving member, the sufficiently wide image flowing is mostly caused by the phenomenon (1), optical band gap and the like are sometime deteriorated, no critical problem occurs in the market. with insufficient removal of the image flowing. However, since the development of an electrophoto In the present invention, the surface layer is formed graphic apparatus provided with no means for heating a by using a material in which the ratio of silicon atoms light-receiving member for the purposes of cost-cutting, each having at least one bond to a carbon atom to the energy saving and the like, and since copying is continu total number of silicon atoms is set to a value which is ously repeated at a higher speed for a longer time than higher than conventional values, so that the above conventional apparatuses, attention is paid to image 65 properties which are opposite to each other can be flowing which is insufficiently removed by the conven satisfactorily improved. tional measures and which is caused by the phenome Further, in the present invention, the surface layer is non (2). formed by using a material in which the ratio of silicon 5,284,730 7 8 atoms each having at least one bond to a carbon atom The substrate used in the present invention may ei and the ratio of silicon atoms each having at least one ther be electroconductive or insulative. Examples of bond to an oxygen atom relative to the total number of electroconductive substrates include metals such as silicon atoms, are respectively specified to values which NiCr, stainless steel, Al, Cr, Mo, Au, In, Nb, Ta, V, Ti, are higher than conventional values so that the weather Pt, Pb, Fe and the like; alloys and laminates thereof and ing resistance and environmental properties can be im the like. proved without the mechanical strength and transpar Examples of the insulating substrates that are gener ency (transmitting an electromagnetic wave having a ally used include films and sheets of synthetic resins desired wavelength) deteriorating, and an electrophoto such as polyester, polyethylene, polycarbonate, cellu graphic light-receiving member having a great effect of O lose acetate, polypropylene, polyvinyl chloride, polyvi preventing toner filming can be achieved. Further en nylidene chloride; polystyrene, polyamides and the like; hanced properties are obtained if the ratio of carbon glass; ceramics, paper. Any one of these insulating Sub atoms having at least one bond to an oxygen atom to the strates preferably has at least one surface which is sub total number of carbon atoms is much higher than con jected to electroconductive treatment. It is desirable to ventional values. 15 provide the light-receiving layer on the thus-treated Although the detailed function of the effect of pre surface. venting toner filming is not clear, it is believed that In the case of glass, for instance, a thin film is formed when the bonding among the silicon, carbon and oxy on the surface of the glass by using at least one material gen atoms is optimum, the formation of weak bonding selected from the group consisting of NiCr,Al, Cr, Mo, 20 Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In2O3, SnO2, ITO (In between the resin in the toner and the surface of the 2O3 + SnO2) and the like so that electroconductivity is light-receiving member, which causes the occurrence provided to the surface. In the case of a synthetic resin of filming, can be minimized. film such as polyester film or the like, a thin film is It is believed that the silicon, carbon and oxygen formed on a surface of the film by vacuum deposition, atoms are nonuniformly distributed in a deposited film. 25 electron beam deposition, sputtering or the like of at Areas of higher concentration of silicon, carbon or least one metal selected from the group NiCr,Al, Ag, oxygen atoms are therefore present in the surface layer. Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt and the Accordingly, the numbers of bonds between the respec like or laminating the surface with at least one of the tive atoms is, in fact, smaller than the values estimated metals so that electroconductivity is provided to the from the proportions of such atoms in the composition 30 surface. The substrate can be formed into a desired of the layer. Therefore, by employing a material in shape such as a cylindrical, belt-like, plate-like shape or which the ratio of the silicon atoms each having at least the like, which can be determined according to desire. one bond to a carbon atom or an oxygen atom and, For example, an endless belt-like or cylindrical shape is preferably wherein the ratio of carbon atoms bonded to preferable for continuous high-speed copying. The oxygen atoms, is substantially higher than conventional 35 thickness of the substrate is appropriately determined so values, that problem is alleviated. that a desired electrophotographic light-receiving In addition, the presence of fluorine atoms provides member can be formed. When the electrophotographic further beneficial effects. The fluorine atoms function, light-receiving member is required to have flexibility, at least in part, to prevent the bonds between the silicon the substrate is made as thin as possible within a range and carbon atoms from being severed by corona dis which allows the function as a substrate to be suffi charge or the like. ciently exhibited. However, in this case, the substrate is A photoconductive member of the present invention generally 10 u or more in view of the production and is described in detail below with reference to the draw handling of the substrate or the mechanical strength ings. thereof, FIG. 1 is a schematic drawing of the layer structure 45 In addition, when an image is recorded by using co of an electrophotographic light-receiving member in herent light such as laser beams, desired irregularities accordance with a preferred embodiment of the present may be provided on a surface of the substrate for the invention. purpose of removing defective images caused by a so The electrophotographic light-receiving member 100 called interference fringe pattern, which is produced in shown in FIG. 1 has a substrate 101 used for a light 50 a visible image. receiving member and a light-receiving layer 102 pro FIGS. 2(A) to 2(C) are schematic sectional views of vided on the substrate 101. The light-receiving layer substrates which respectively show examples of irregu 102 has a photoconductive layer 103 which is made of larities. A-Si(H,X) (a silicon-based non-single crystal material When irregularities are provided on a surface of the containing hydrogen and/or halogen atoms) and which 55 substrate, a cutting tool having a V-shaped cutting edge has photoconductivity, and surface layer 104 which is is fixed to a predetermined position of a cutting machine made of non-single crystal material containing silicon such as a milling machine, a lathe or the like. For exam and carbon atoms. In the surface layer 104, at least a ple, a cylindrical substrate is regularly moved in a pre surface-side region thereof contains a ratio of at least determined direction while being rotated according to a 50% silicon atoms each having at least one bond to a program so that the surface of the substrate can be carbon atom relative to the total number of silicon accurately cut to form irregularities with a desired atoms in the surface layer and the ratio of silicon atoms shape, pitch and depth. The reverse V-form linear pro each having at least one bond to an oxygen atom rela jecting portion of the irregularities formed by the above tive to the total number of silicon atoms therein is from cutting method has a helical structure along the axis of 10 to 30 atomic percent. In addition, it is preferred that 65 the cylindrical substrate. The helical structure of the the ratio of carbon atoms bonded to oxygen atoms rela reverse V-form linear projecting portion may be a dou tive to the total number of atoms is from 10 to 30 atomic ble or treble helical structure or a cross-helical struc percent. tle. 5,284,730 10 Further, a delay line structure along the axis may be substrate in the electrophotographic light-receiving added to the helical structure. member of the present invention are described with The cross-sectional form of the convex portion of the reference to FIG. 4, the shape and production method irregularities provided on the surface of the substrate for the substrate in the light-receiving member of the preferably is a reverse V-form so as to ensure that there invention are not limited to them. is controlled unevenness of the thickness in a minute FIG. 4 is a schematic drawing of a typical example of column for each of the layers formed, and good adhe the shape of the substrate surface in the electrophoto sion and desired electrical contact properties between graphic light-receiving member according to the pres the substrate and the layer provided directly thereon. ent invention in which an irregular portion is enlarged. However, as shown in FIG. 2, the sectional form of the O In FIG. 4, reference numeral 1601 denotes a sub convex portion is preferably substantially an equilateral strate; reference number 1602, a surface of the substrate; triangle, a right-angled triangle or an unequilateral tri reference numeral 1603, a rigid sphere; and reference angle. Of these forms, an equilateral triangle and right numeral 1604, a spherical dimple. angled triangle are most preferable. FIG. 4 also shows a preferred example of methods of In the present invention, the dimensions of the irregu 5 obtaining the surface shape of the substrate. Namely, larities provided in the surface of the substrate in a FIG. 4 shows that the spherical recess 1604 can be controlled state are determined in consideration of the formed by causing the rigid sphere 1603 to gravitation points below so that the object of the present invention ally fall from a position at a predetermined height from can be consequently achieved. the substrate surface 1602 so that the sphere 1603 col That is, firstly, the amorphous silicon (A-Si (H,X)) 20 lides against the surface 1602 of the substrate. A plural which contains hydrogen and/or halogen atoms and ity of spherical dimples 1604 having substantially the which forms the light-receiving layer is sensitive to the same radius of curvature R and the same width D can state of the surface on which the layer is formed, and be formed on the surface 1602 of the substrate by caus the layer quality significantly depends upon the surface ing a plurality of the rigid spheres 1603 having substan State. 25 tially the same radius R, to simultaneously or succes It is therefore necessary to determine the dimensions sively fall from substantially the same height h. of the irregularity provided on the surface of the sub FIG. 5 shows a typical example of the substrates strate so that the quality of the A-Si (H,X) layer does formed with irregularities comprising a plurality of not deteriorate. spherical dimples formed on the surface thereof as de Secondly, if the free surface 105 of the light-receiving 30 scribed above. layer has extreme irregularities, the image formed can The radius of curvature R and width D of each of the not be completely cleaned during the cleaning process spherical dimples which form the irregular form of the after the formation thereof. surface of the substrate of the electrophotographic There is also the problem that in the case of cleaning light-receiving member of the invention are important with a blade, the blade is easily damaged. 35 factors for efficiently achieving the effect of preventing As a result of investigation of the problems with the occurrence of interference fringe pattern which is respect to the formation of a layer, the problems with confirmed in the image printed by the light-receiving respect to the electrophotographic process and condi member according to the present invention. As a result tions for preventing the occurrence of an interference of experiments performed by the inventors, the inven fringe pattern, the pitch of the concave portions on the tors found the following facts: surface of the substrate is preferably 500 to 0.3 un, When the radius R of curvature and width D satisfy more preferably 200 to 1 um, most preferably 50 to 5 the following equation: im. The maximum depth of the concave portions is pref. erably 0.1 to 5um, more preferably 0.3 to 3 um, most 45 20.035 preferably 0.6 to 2 um. When the pitch and the maxi mum depth of the concave portions are within the at least 0.5 Newton ring is produced in each of the above ranges, the inclination of the slope of each con dimples by the shearing interference. cave portion (or linear projecting portion) is preferably When R and D satisfy the following equation: 1 to 20, more preferably 3 to 15, most preferably 4 to 50 10. The maximum difference in thickness based on nonu 20,055 niformity in the layer thickness of each of the layers deposited on the substrate is preferably 0.1 to 2 um, at least one Newton ring is produced in each of the more preferably 0.1 to 1.5um, most preferably 0.2 to 1 55 dimples by the shearing interference. um, within the same pitch. This finding shows that the D/R value is at least In another method of removing defective images 0.035, preferably at least 0.055, for dispersing the inter caused by an interference fringe pattern when coherent ference fringes produced in the whole light-receiving light such as laser beams or the like is used, irregularities member in each of the dimples, thereby preventing the are provided by forming a plurality of fine spherical occurrence of interference fringes confirmed in the dimples on the surface of the substrate. image printed by using the light-receiving member. Namely, the size of the irregularities which are com The width D of each of the dimples which form posed of a plurality of the fine spherical dimples and irregularities is at most about 500 um, preferably 200 which are formed on the surface of the substrate is um or less, more preferably 100 um or less. smaller than the resolving power required for the elec 65 In the present invention, the photoconductive layer trophotographic light-receiving member. 103 which is formed on the substrate 101 and which Although the shape of the surface of the substrate and partially forms the light-receiving layer 102 has the a preferable example of the methods of producing the semiconductor properties below and is made of A-Si 5,284,730 11 12 (H,X) showing photoconductivity for the light applied taining halogen atoms, silicon halide gas used as raw thereto. material gas for supplying Si and gases such as Ar., H2, (1) p-type A-Si (H,X)-containing an acceptor only He or the like are introduced, at a predetermined mixing or both the acceptor and a donor in which the ratio and flow rates, into the deposition chamber for relative content of the acceptor is higher. forming the photoconductive layer, and a plasma atmo (2) p-type A-Si (H,X)-in Type (1), the content sphere is formed by inducing glow discharge so that the (Na) of the acceptor is lower, or the relative con photoconductive layer can be formed on a predeter tent of the acceptors is lower. mined substrate. In this embodiment, a predetermined (3) n-containing a donor only or both the donor and amount of silicon compound gas containing hydrogen an acceptor in which the relative content of the O atoms may be further mixed with the above gas mixture donor is higher. for the purpose of supplying hydrogen atoms. (4) n-type A-Si (H,X)-in Type (3), the content The above gases may be used singly or in a mixture of (Nd) of the donor is lower, or the relative content a plurality of gases with a predetermined mixing ratio. of the acceptor is lower. A layer of A-Si (H,X) can be formed by the reaction (5) i-type A-Si (H,X)-Naa...Nda-O or Naa-Nd 15 sputtering or ion plating process. In the sputtering pro In the present invention, F, Cl, Brand I are preferable cess, a Si target is sputtered in a predetermined gas as a halogen atom (X) contained in the photoconductive plasma atmosphere. In the ion plating process, a poly layer 103, and F and Clare particularly preferable. crystal silicon or single crystal silicon received as an In the present invention, the photoconductive layer evaporation source in an evaporation chamber is heated 103 made of A-Si (H,X) is formed by a vacuum deposi 20 and evaporated by a resistance heating method or an tion method which employs a discharge phenomenon, electron beam (EB) method, and the evaporated sub for example, a glow discharge process, a microwave stance is passed through a predetermined gas plasma discharge process, a sputtering process, an ion plating atmosphere. process or the like. For example, when an amorphous When the halogen atoms are introduced into the layer layer made of A-Si (H,X) is formed by the glow dis 25 formed by the sputtering process or the ion plating charge process, Si supplying raw material gas which process, gas of the halogen compound or silicon com can supply silicon atoms (Si) and raw material gas for pound containing halogen atoms may be introduced supplying hydrogen atoms (H) and/or halogen atoms into the deposition chamber to form a plasma atmo (X) are introduced into a deposition chamber in which sphere of the gas. the pressure can be reduced, and glow discharge is When hydrogen atoms are introduced into the layer, induced in the deposition chamber so that the layer of raw material gas for supplying hydrogen atoms, e.g., A-Si (H,X) is formed on a predetermined surface of a H2 or the above silanes, may be introduced into the substrate placed at a predetermined position. When sputtering deposition chamber to form a plasma atmo such a layer is formed by the sputtering process, gas for sphere of the gas. supplying hydrogen atoms (H) and/or halogen atoms 35 In the present invention, although any one of the (X) may be introduced into a sputtering deposition halogen compounds and halogen-containing silicon chamber during sputtering of a Si target in an atmo compounds is effectively used as raw material gas for sphere of inert gas such as Air, He or the like or a gas supplying halogen atoms, other examples of compounds mixture based on the inert gases. that can be effectively used as a starting material for Examples of gases that are effectively used as raw forming the photoconductive layer include hydrogen material gases for supplying Si in the present invention halides such as HF, HCl, HBr, HI and the like, halogen include silicon hydrides (silanes) such as SiH4, Si2H6, substituted silicon hydrides such as SiH2F2, SiH22, Si3H8, and the like, all of which are gaseous or can be SiH2Cl2, SiHC3, SiH2Br2, SiHRrs and the like, all of gasified. SiH4 and Si2H6 are particularly preferable from which are gaseous or can be gasified and which contain the viewpoints of ease of handling in the work of form 45 hydrogen atoms as a component. ing a layer, high efficiency of Si supply and the like. In the present invention, such halogen compounds Preferable examples of raw material gases effectively containing hydrogen atoms are preferably used as raw used for supplying halogen atoms in the present inven materials for supplying halogen atoms because hydro tion include many halogen compounds such as halogen gen atoms which are extremely effective for controlling gas, halides, compounds, halogen-sub 50 electrical or photoelectric properties are introduced stituted silane derivatives and the like, all of which are into the layer at the same time as the introduction of gaseous or can be gasified. halogen atoms during the formation of the layer. Silicon compounds which consist of silicon and halo Halogen atoms can also be structurally introduced gen atoms, which are gaseous or can be gasified and into the layer by causing gas of H2 or a silicon halide which contain halogen atoms can also be exemplified as 55 such as SiH4, Si2H6, Si2H8, SiH0 or the like to coexist effective compounds in the present invention. with a silicon compound for supplying Si in the deposi Typical examples of halogen compounds that can be tion chamber and inducing discharge therein. preferably used in the present invention include halogen For example, in the reaction sputtering process, gas gases such as fluorine, chlorine, bromine, iodine and the for supplying halogen atoms, H2 gas and, if required, like, and interhalogen compounds such as BrF, ClF, 60 inert gas such as He, Ar or the like, are introduced into ClF3, BrFs, BrF3, IF, IF, IC, IBr and the like. the deposition chamber, and a plasma atmosphere is Typical examples of silicon compounds containing formed therein so that a layer of A-Si (H,X) can be halogen atoms, i.e., halogen-substituted silane deriva formed on a substrate by sputtering the Si target used. tives, include silicon halides such as SiF4, Si2F6, SiCl4, B2H6 gas or the like may be further introduced for SiBI and the like. 65 doping the layer with impurities. When the photoconductive member which is charac The amount of hydrogen atoms (H), the amount of teristic of the present invention is formed by the glow halogen atoms (X) or the total of hydrogen and halogen discharge process using such a silicon compound con atoms, which are contained in the photoconductive 5,284,730 13 14 layer of the electrophotographic light-receiving mem include saturated hydrocarbons having 1 to 4 carbon ber formed in the present invention is preferably 1 to 40 atoms, hydrocarbons of ethylene series having 2 to 4 atomic %, more preferably 5 to 30 atomic 9%. carbon atoms, hydrocarbons of acetylene series having The amount of hydrogen atoms (H) and/or halogen 2 to 3 carbon atoms and the like. atoms (X) contained in the layer may be controlled by, Typical examples of such saturated hydrocarbons for example, controlling the temperature of the sub include methane (CH4), ethane (C2H6), propane (C3H8), strate used and/or the amount of the starting material n-butane (n-C4H10), pentane (C5H12) and the like. Typi introduced into the deposition apparatus for introduc cal examples of hydrocarbons of ethylene series include ing hydrogen atoms (H) or halogen atoms (X) in the ethylene (C2H4), propylene (C3H6), butene-1 (C4Hs), layer, discharge power or the like. 10 butene-2 (C4H8), isobutylene (C4H8), pentene (C5H10) Preferable examples of dilution gases which are used and the like. Typical examples of hydrocarbons of acet for forming the photoconductive layer by the glow ylene series include acetylene (C2H2), methylacetylene discharge or sputtering process in the present invention (C3H4), butyne (C4H6) and the like. include rare gases such as He, Ne, Ar and the like. Alkyl silicides such as Si(CH3)4, Si (C2H4)4 and the A desired property of the above semiconductor prop 15 like can be exemplified as raw material gas consisting of erties 1 to 5 can be imparted to the photoconductive Si, C and H atoms. layer 103 by doping the layer formed with n-type impu Examples of oxygen-containing compounds that can rities, p-type impurities or both types of impurities be used as raw material for introducing oxygen atoms while controlling the amount of impurities during the include oxygen (O2), carbon monoxide (CO), carbon formation of the layer. 20 dioxide (CO2), nitrogen monoxide, nitrogen dioxide and Preferable examples of p-type impurities include the like. atoms such as B, Al, Ga, In, Tl and the like which be Examples of nitrogen-containing compounds that can long to the Group III in the Periodic Table. Preferable be used as raw material for introducing nitrogen atoms examples of n-type impurities include atoms such a N, include nitrogen (N2), nitrogen monoxide, nitrogen P, As, Sb, Bi and the like which belong to the Group V 25 dioxide, ammonia and the like. of the Periodic Table. B, Ga, P and Sb are particularly For example, when the photoconductive layer is preferable. formed by the sputtering process, sputtering may be In the present invention, the amount of impurities performed by using a sputtering target made of a mix which are doped in the photoconductive layer 103 for ture of (Si-Si3N4), (Si-SiC), or (Si-SiO2) with a the purpose of obtaining a desired conduction type is 30 desired mixing ratio or using a target comprising a Si appropriately determined according to desired electri wafer and a Si3N4 wafer, a Si wafer, a SiC wafer or a Si cal and optical properties. In the case of impurities in wafer and a SiO2 wafer. Alternatively, the photocon the Group III in the Periodic Table, the amount of the ductive layer may be formed by sputtering Sior a target impurities doped may be 3x 10-3 atomic % or less. In in the deposition chamber in which gas of a compound the case of impurities in the Group V in the Periodic 35 containing carbon, nitrogen or oxygen is introduced Table, the amount of the impurities doped may be together with sputtering gas such as Argas or the like. 5X10-3 atomic 7% or less. Since the amount of carbon, oxygen or nitrogen The photoconductive layer 103 may be doped with which is contained in the photoconductive layer formed impurities by introducing a raw material for introducing in the present invention has a significant effect on the impurities into the deposition chamber together with characteristics of the electrophotographic light-receiv the main raw material used for forming the photocon ing member produced, the amount must be appropri ductive layer 103 during formation thereof. It is desir ately determined according to demands. However, the able to use as such raw material for introducing impuri amount is preferably 0.0005 to 30 atomic %, more pref. ties a substance which is gaseous at room temperature erably 0.001 to 20 atomic %, most preferably 0.002 to 15 and atmospheric pressure and which can easily be gas 45 atomic 2. ified at least under conditions for forming the layer. The thickness of the photoconductive layer 103 is It is also desirable to appropriately combine A-Si appropriately determined according to desire so that (H,X) of the types selected from the types (1) to (5) of the photocarriers generated by irradiation of light hav the A-Si (H,X) layer in view of charge polarity or the ing desired spectral properties are efficiently trans like, as occasion demands. 50 ported. The thickness is generally 1 to 100 u, preferably Typical examples of starting materials used for intro 2 to 50 u. ducing impurities include PH3, P2H4, PF3, PFs, PCl3, The surface layer 104 formed on the photoconduc AsH3, AsF3, AsF5, AsCl3, SbH3, SbF3, SbF5, BiH3, tive layer 103 has the free surface 105 which is provided BF3, BCl3, BBr3, B2H6, B4H10, B5H9, B5H11, B6H10, for achieving the objects of the present invention with B5H12, B4H14, AlCl3, GaCl3, InCl3, TiCl3 and the like. 55 respect to the humidity resistance, continuous repeated For example, when the photoconductive layer is service properties, electrical voltage resistance, work formed by the glow discharge process, in order to con ing environmental properties and durability. tain atoms of at least one kind of carbon, oxygen and In addition, in the present invention, since the amor nitrogen atoms, in the photoconductive layer, a com phous materials respectively used for forming the pho pound containing at least one kind of carbon, oxygen toconductive layer 103 and the surface layer 104, which and nitrogen atoms may be introduced, together with form the light-receiving layer 102, have a common the raw material gas for forming the photoconductive component, i.e., silicon atoms, chemical stability is suffi layer, into the deposition chamber which allows the ciently ensured at the interface between both layers. pressure to be decreased, and glow discharge may be As a matter of course, there is no clear interface be induced in the deposition chamber so that the photo 65 tween the photoconductive layer 103 and the surface conductive layer can be formed. layer 104. Namely, the content of the carbon atoms in Examples of carbon-containing compounds that can the photoconductive layer 103 may be gradually in be used as raw material for introducing carbon atoms creased from the outer side thereof so that a desired 5,284,730 15 16 ratio of bonding between silicon and carbon atoms is like. However, in any one of the processes, as described attained at least in the region on the surface side. above, the layer is formed by controlling reaction so Having no clear interface between the photoconduc that the ratios of the number of silicon atoms each hav tive layer 103 and the surface layer 104 is preferable ing at least one bond to a carbon atom and the number when coherent light such as laser beams or the like is 5 of silicon atoms each having at least one bond to an used as a light source because the refractive index is oxygen atom relative to the total number of silicon changed or reflection is produced at the interface. atoms in the surface layer are different from those in The numerical range of the thickness of the layer conventional members. according to the invention is also an important factor Like the RF discharge process and microwave dis for effectively achieving the object of the invention. O charge process, an example of the methods of control The numerical range of the thickness of the layer ling the bonding of silicon atoms in the plasma CVD according to the invention is appropriately determined process is a method of selecting the types of raw mate according to the desired purposes so that the objects of rial gases and employing the ions produced by applying the invention can be effectively achieved. an electrical field during discharge. In regard to the thickness of the photoconductive 5 In a method of controlling the reaction so that the layer 103, it is also necessary to appropriately determine number of silicon atoms each having at least one bond the thickness of the surface layer 104 according to de to a carbon atom in the surface layer relative to the total sire on the basis of the organic connection correspond silicon atoms therein is greater than a conventional ing to the properties required for each of the layer re value, it is particularly effective for the microwave gions. In addition, it is preferable to consider economy 20 discharge process to use as raw material gases silicon including productivity and mass productivity. containing gas such as silane (SiH4), silicon tetrafluoride The thickness of the surface layer 104 in the present (SiF4) or the like, and/or carbon-containing gas such as invention is generally 0.003 to 30 u, preferably 0.004 to methane (CH4), (CF4) or the like 20 u, and more preferably 0.005 to 10 u. When no clear and an alkyl silicide such as interface is present between the photoconductive layer 25 (Si(CH3)4), tetraethylsilane (Si(C2H4)4 or the like. 103 and the surface layer 104, the thickness of the re Its is also effective to excite the gas used as carbon gion of a-(Six.C.O.).H.F within the above range may containing gas and having a double or triple bond, to be considered as the thickness of the surface layer 104 gether with silicon-containing gas, by using light, an for convenience's sake. electrical field or the like. The thickness of the light-receiving layer of the elec 30 In the microwave discharge process, the controlling trophotographic light-receiving member 100 in the effect is improved by applying an electrical field to the present invention is appropriately determined so as to discharge space so as to effectively bring ions near the meet the desired purpose. surface of the substrate in the above method. In the present invention, the thickness of the light Under these conditions, the supply of the raw mate receiving layer 102 is appropriately determined on the 35 rial gas containing oxygen atoms permits control of the basis of the relation between the thicknesses of the pho reaction so that the ratio by number of silicon atoms toconductive layer 103 and the surface layer 104 so as to each having at least one bond to an oxygen atom to the make effective use of each of the properties imparted to total silicon atoms in the surface layer is greater than the photoconductive layer 103 and the surface layer that obtained by discharge simply using microwave. 104, both of which form the light-receiving layer 102, 40 This phenomenon can be more effectively performed and effectively achieve the object of the present inven by changing the material gas used for supply oxygen, tion. The thickness of the light-receiving layer 102 is In the present invention, at least one gas containing preferably determined so that the thickness of the pho hydrogen atoms and at least one gas containing fluorine toconductive layer 103 is at least several thousand times atoms are used as raw material gases for providing hy the thickness of the surface layer 104. 45 drogen and fluorine atoms in surface layer 104. Exam The typical value of the thickness is generally 3 to ples of gases containing hydrogen atoms include silane 100 u, preferably 5 to 70 u, and more preferably 5 to 50 (SiH4), methane (CH4), hydrogen (H2) and the like. L. Examples of gases containing fluorine atoms include In the electrophotographic light-receiving member of silicon tetrafluoride (SiF4), carbon tetrafluoride (CF4) the present invention, an adhesive layer made of an 50 and the like. amorphous material such as Si3H4, SiO2, SiO or the like, As a method of controlling reaction so that the ratio which contains at least one of hydrogen and halogen by number of silicon atoms each having at least one atoms, at least one of nitrogen and oxygen atoms and a bond to a carbon atom in the surface layer to the total silicon atom, may be provided between the substrate silicon atoms therein is small, it is effective for the mi 101 and the photoconductive layer 103 for the purpose 55 crowave discharge process to use saturated bond spe of further improving the adhesion therebetween. cies in which a plurality of silicon atoms or carbon It is also preferable to provide a layer or region con atoms are combined. For example, disilane (Si2H6), taining Ge on the side of the substrate for the purpose of disilicon hexafluoride (Si2F6) or the like is used as the effectively absorbing light with a long wavelength such raw material gas for silicon atoms, and ethane (C2H6), as infrared laser beams. 60 propane (C3H8) or the like is used as the raw material As described above, the surface layer 104 may be gas for carbon atoms. made of a non-single crystal material A- (SixCO2)- When oxygen atoms are further contained in the HF) containing silicon, carbon, oxygen, fluorine and layer, it is also preferable to determine the amount of hydrogen atoms. In this case, an attempt can be made to the alkyl silicide introduced relative to the total amount improve a measure against filming. 65 of the silicon-containing gas and carbon-containing gas The surface layer 104 made of A- (SiC.O.).H.F, can which are introduced into the film-forming space so as also be formed by the RF discharge process, the micro to be within the above-described range. However, if the wave discharge process, the sputtering process or the ratio of bonding between oxygen and silicon atoms is 5,284,730 17 18 within a desired range, there is no need for controlling the formation of the surface layer 104 is appropriately the amount of the alkyl silicide introduced so that it is selected from the optimum temperature range for the within the above range. method of forming the surface layer 104. The tempera As a method of controlling reaction so that the ratio ture of the substrates is generally 50 to 400° C., prefera by number of carbon atoms each having at least one 5 bly 100 to 350° C. It is advantageous for forming the bond to an oxygen atom in the surface layer to the total surface layer 104 to employ the glow discharge presses carbon atoms therein is greater than conventional val or the sputtering process because the precise control of ues, it is effective for the microwave discharge process the component ratios of the constituent atoms of the to use silicon-containing gas such as silane (SiH4), sili layer and the control of the thickness of the layer are contetrafluoride (SiF4) or the like, and/or oxygen-con- 10 relatively easy, as compared with other processes. taining gas such as oxygen (O2), water (H2O), nitrogen However, when the surface layer 104 is formed by the monoxide (NO) or the like and a compound such as above process, the discharge power and gas pressure carbon monoxide (CO), carbon dioxide (CO2), ethyl during formation of the layer are important factors ether (CH3)2O or the like, which contain both carbon which influence the properties of A- (SiC.O.).H.F. and oxygen. 15 formed, like the temperature of the substrate. In the present invention, examples of dilution gases The condition of the discharge power for effectively that can be used for forming the surface layer include forming, with high productivity, A- (SiCO2).H.Fy hydrogen (H2), argon (Ar), helium (He) and the like. having properties which enable the achievement of the It is also effective for the present invention to intro object of the invention is generally 10 to 5,000W, pref. duce a nitrogen-containing gas such as nitrogen (N2), 20 erably 20 to 2,000W, per substrate. In the RF discharge ammonia (NH3), or the like, a fluorine compound such process, the gas pressure in the deposition chamber is as (GeF4), nitrogen fluoride generally 0.01 to 2 Torr, preferably 0.1 to 1 Torr. In the (NF3) or the like, a gas mixture thereof or dopant gases microwave discharge process, the gas pressure is gener such as diborane (B2H6), boron fluoride (BF3), phos ally 0.2 to 100 mTorr, preferably about 1 to 50 mTorr. phine (PH3) or the like during the formation of the 25 Although the preferable numerical ranges of the ten surface layer 104. perature of the substrate and the discharge power for The surface layer 104 according to the present inven forming the surface layer 104 in the invention are de tion is carefully formed in consideration of the ratio of scribed above, the factors for forming the layer are not bonds between silicon and carbon atoms and the ratio of separately determined, but the optimum value of each bonds between silicon and oxygen atoms or both ratios 30 of the factors for forming each layer is preferably deter and the ratio of bonds between carbon and oxygen mined on the basis of the mutual organic connection so atoms so that the required properties are obtained ac that the surface layer of A- (SixCO).H.F having de cording to demands. sired properties can be formed. Namely, substances consisting of Si, C, O, F and H The amount of hydrogen atoms contained in the sur respectively have structural forms ranging from crystal 35 face layer 104 of the electrophotographic light-receiv to amorphous, electrical properties ranging from con ing member in the invention is generally 41 to 70 atomic ductive to semiconductive and insulative, and proper %, preferably 45 to 60 atomic %, of the total constituent ties ranging from photoconductive to non-photocon atoms. When the hydrogen content is within the above ductive, depending upon the conditions for formation ranges, the light-receiving member formed is signifi thereof. In the present invention, therefore, the condi- 40 cantly superior to conventional members in practical tions for formation of A-(SiC.O.).H.Fy are strictly use and thus can be satisfactorily used. selected according to desire so that the substance hav Namely, it is generally know that the properties of ing desired properties is formed in correspondence with the electrophotographic light-receiving member are the desired purpose. adversely affected by the defects (mainly dangling For example, if the surface layer 104 is provided for 45 bonds of silicon and carbon atoms) which are present in the purpose of improving the voltage resistance, A-(Six the surface layer made of A- (SiCO).H.F. For exam CyO2).H.Fy is formed as a non-single crystal material ple, the charge properties are deteriorated due to the showing significant electrical insulating behavior in the injection of charge from the free surface or changed due working environment. to changes in the surface structure in the working envi If the surface layer 104 is provided for the purpose of 50 ronment, e.g., under high humidity. The after image improving the continuous repetitive working properties phenomenon occurs during repetitive use due to trap and working environmental properties, A-(SiCO)- ping of charge in the defects of the surface layer from HFy is formed as a non-single crystal material having the photoconductive layer during corona discharge or a degree of electrical insulating properties which is irradiation of light. decreased to some extent and a certain degree of sensi- 55 However, the amount of the defects in the surface tivity to the light applied thereto. layer can be significantly decreased by controlling the When the surface layer 104 made of A- (SiCO)- hydrogen content in the surface layer to be at least 41 HF is formed on the surface of the photoconductive atomic %. As a result, all the above-described problems layer 103, the temperature of the substrate during the can be solved, and the electrical properties and high formation of the layer is an important factor which 60 speed continuous usability can be significantly in influences the structure and properties of the layer proved, as compared with conventional members. formed. In the present invention, it is preferable to care On the other hand, if the hydrogen content in the fully control the temperature of the substrate during the surface layer exceeds 70 atomic %, the hardness of the formation of the layer so that A- (SiCO).H.F having surface layer is decreased, and thus the member cannot the intended properties can be formed according to 65 sufficiently resist repetitive use. It is therefore important desire. for obtaining excellent electrophotographic properties In order to effectively achieve the object of the pres to control the hydrogen content in the surface layer so ent invention, the temperature of the substrate during that the content is within the above range. The hydro 5,284,730 19 20 gen content in the surface layer can be controlled by In the present invention, the numerical range of the using the flow rate of H2 gas, the temperature of the thickness of the layer is an important factor for effec substrate, the discharge power, the gas pressure or the tively achieving the object of the invention. Although like. any numerical range can be selected as the range of the The content of fluorine atoms in the surface layer is 5 thickness of the surface layer (or the surface-side re generally from about 0.1 to 10 atomic %, preferably gion) 104 made of A- (SiCO).H.F which satisfies the from about 0.6 to 4 atomic 9%. The content of fluorine above relations according to the desired properties, a atoms in the surface layer is at least about 0.1 atomic % preferable range is 10 to 500 A. Namely, if the thickness or more, so that the bonds between silicon and carbon is less than 10 A, the objects of the present invention are atoms can be effectively produced in the surface layer. 10 insufficiently obtained and the surface layer is some The fluorine atoms in the film function to effectively times lost due to abrasion or the like during the use of prevent the bonds between silicon and carbon atoms the light-receiving member. If the thickness exceeds 500 from being severed due to damage caused by the corona A, the electrophotographic properties sometimes dete or the like. riorate, for example, the residual potential is increased. On the other hand, if the content of fluorine atoms in 15 In the present invention, it is also effective for further the surface layer exceeds about 10 atomic %, there is improving the properties such as the chargeability or almost no recognizable enhancement in the production the like by providing a blocking layer (lower surface of bonds between the silicon and carbon atoms in the layer) or a blocking region (lower surface region), surface layer and there is effective prevention of the which is made of SiC (H,X) and which contains oxygen severing of bonds between the silicon and carbon atoms 20 atoms in a reduced amount, between the photoconduc (primarily due to the damage caused by corona or the tive layer and the surface layer or in the surface layer. like). In addition, since the presence of excessive In the electrophotographic light-receiving member of amounts of fluorine atoms can inhibit the movement of the present invention, an adhesive layer made of Si3N4, carriers in the surface layer, a significant residual poten SiO2, SiO or a non-single crystal material containing at tial or image memory can be produced. It is, therefore, 25 least one of hydrogen and halogen atoms, at least one of very important for obtaining the desired enhanced elec nitrogen and oxygen atoms and a silicon atom may be trophotographic properties to control the content of provided between the substrate 101 and the photocon fluorine atoms in the surface layer to be preferably ductive layer 103 for the purpose of further improving within the above range. The content of fluorine atoms the adhesion therebetween, like the above-described in the surface layer can be controlled by controlling the 30 example. flow rate of fluorine-containing gas, such as silicon In the embodiment of the surface layer 104 made of tetrafluoride or the like, the temperature of the sub A- (SiCO).H.F, the component ratios may be gradu strate, the discharge power, the gas pressure or the like. ally changed so that no clear interface is present be It the atomic composition of the surface layer in the tween the photoconductive layer 103 and the surface present invention is expressed by the formula A- (Sig 35 layer 104 to obtain the surface layer 104 having the CO).H.F. it is preferable that q is 0.1 to 0.4, r is 0.4 to desired component ratios. 0.7, s is 0.05 to 0.2 (wherein q+r-s= 1), t is 0.3 to 0.59, As a matter of course, in this embodiment, the pro u is 0.41 to 0.7, v is 0.001 to 0.1 (wherein t-i-u-- v = 1). duction conditions are selected so as to satisfy each of In the present invention, however, any atoms other than the above requirements. the above atoms can be contained in the surface layer so 40 A description will now be made of the method of far as the contents are low (preferably 10 atomic % or producing the photoconductive member by the micro less, more preferably 3 atomic % or less, and most pref. wave discharge process. erably atomic 76 or less). FIGS. 6 and 7 show the apparatus for producing the If the composition of the surface layer is beyond the electrophotographic light-receiving member by the above ranges, any one of the strength, transparency, 45 microwave discharge process using a cylindrical sub durability and weathering resistance of the surface layer strate. In the drawings, reference numeral 1101 denotes deteriorates, and the effect of the present invention are a reactor having a structure which can be made airtight significantly decreased. under vacuum. Reference numeral 1102 denotes a mi In the present invention, the bonding state of silicon crowave introducing dielectric window which effi atoms in the surface layer is a very important factor. In 50 ciently transmits microwave power to the reactor 1101, order to obtain the objects of the invention, the content and which is made of a material (for example, quartz of the silicon atoms each having at least one bond to a glass, alumina ceramics or the like) which can hodl the carbon atom is within the range of 50 to 100%, prefera airtight vacuum state. Reference numeral 1103 denotes bly 60 to 100%, and more preferably 70 to 100%, of the a waveguide for transmitting microwave power which total number of silicon atoms in the surface layer, and 55 comprises a rectangular portion extended from a micro the content of the silicon atoms each having at least one wave power source to a position near the reactor 1101 bond to an oxygen atom is preferably within the range and a cylindrical portion inserted into the reactor 1101. of 10 to 30% of the total number of silicon atoms in the The waveguide 1103 is connected to the microwave surface layer. power source (not shown) together with a stab tuner If the bonding state is beyond any one of the above 60 (not shown) and an isolator (not shown). The dielectric ranges, the effect of the present invention, particularly, window 1102 is hermetically sealed to the inner wall of the effect of preventing toner filming, deteriorates. the cylindrical portion of the waveguide 1103 so as to In addition, the content of carbon atoms each having hold the atmosphere in the reactor 1101. Reference at least one bond to an oxygen atom is within the range numeral 1104 denotes an exhaust pipe having an end of 10 to 30% of the total number of carbon atoms in the 65 opened to the reactor 1101 and the other end communi surface layer so that the objects of the invention, partic cating with an exhauster (not shown). Reference nu ularly, the object of preventing toner filming, can be meral 1106 denotes a discharge space surrounded by more satisfactorily achieved. substrates 1105. A power source 1111 is a DC power 5,284,730 21 22 source (bias power source) and is electrically connected The amount of carbon atoms or oxygen atoms con to an electrode 1112 for the purpose of applying a DC tained in the second layer region formed can be con voltage to the bias electrode 1112. trolled by, for example, changing the ratio among the The electrophotographic light-receiving member is flow rates of silane gas, methane gas and oxygen gas produced by the above production apparatus according which are introduced into the discharge space. The to the method below. The air in the reactor 1101 is state of bonding of silicon atoms can be arbitrarily con exhausted by a vacuum pump (not shown) through the trolled by displacing silane gas and methane gas by exhaust pipe 1104 so that the pressure in the reactor tetramethylsilane gas and oxygen gas by nitrogen mon 1101 is adjusted to 1 x 10-7 Torr or less. Each of the oxide gas. The state of bonding carbon atoms can be substrates 1105 is then heated to a predetermined tem O arbitrarily controlled by displacing methane gas and perature by a heater 1107. Raw material gases for a first oxygen gas by methyl ether gas. In addition, the bond layer are introduced through gas introducing means ing state can be more effectively controlled by changing (not shown). Namely, raw material gases such as silane the bias voltage applied to the discharge space. The gas as raw material gas for A-Si (H,X), diborane gas as amounts of the hydrogen and fluorine atoms contained doping gas and helium gas as dilution gas are introduced 15 in the second layer region can be controlled according into the reactor 1101. At the same time, a microwave to desire by, for example, arbitrarily changing the flow with a frequency of 2.45 GHz is generated from the rates of hydrogen gas and silicon tetrafluoride gas intro microwave power source (not shown) and introduced duced into the discharge space. into the reactor 1101 through the microwave introduc 20 EXAMPLE 1. ing dielectric window 1102 through the waveguide An electrophotographic light-receiving member was 1103. A DC voltage is applied to the bias electrode 1112 formed on a planished aluminum cylinder by using the from the DC power source 1111 electrically connected production apparatus shown in FIGS. 6 and 7. The to the bias electrode 1112 in the discharge space 1106 so conditions for the formation of a photoconductive layer as to be applied to the substrates 1105. The raw material 25 and a surface layer were as shown in Table 1. In regard gases in the discharge space 1106 surrounded by the to the surface layer, the flow rates of silane gas, methane substrates 1105 are thus excited and dissociated by the gas and tetramethylsilane gas were changed for chang energy of the microwave. The substrates 1105 are sta ing the ratio of silicon atoms bonded to carbon atoms to tionarily subjected to ion impact by the electrical field produce light-receiving members (referred to as between the bias electrode 1112 and the substrates 1105 "drums' hereinafter) under the six different conditions to form a first layer region on the surface of each of the A to F, as shown in Table 2. In addition, separate sur substrates 1105. During this time, each of the substrates face layers only (referred to as "samples' hereinafter) 1105 is rotated around the axis in the direction of the were formed on the same cylinder by using the same generating line thereof by using a motor for rotating a apparatus as that shown in FIGS. 6 and 7. rotation shaft 1109 on which each of the substrates 105 35 The drum was set in an electrophotographic appara is installed so that a deposited film layer is uniformly tus (produced by converting NP7550 manufactured by formed over the whole periphery of the substrates 1105. Canon Inc. for tests in the invention). The initial elec When the second layer region is formed on the thus trophotographic properties such as chargeability, sensi formed first layer region, discharge is started by the tivity, image flowing in high-humidity environment same method as that employed for forming the first 40 (atmospheric temperature: 31 C., humidity: 85%), re layer region with the exception that the composition of sidual potential, ghost, image defect and the like were raw material gas introduced into the reactor 1101 is evaluated under various conditions. The drum was then changed to, for example, silane gas, methane gas, silicon subjected to an endurance test in which printing on tetrafluoride gas, tetramethylsilane gas and, if required, 500,000 sheets was performed at atmospheric tempera hydrogen gas as dilution gas. 45 ture of 33 C. and humidity 90% without using drum The amount of carbon atoms contained in the second heating means such as a drum heater or the like, and the layer region formed can be controlled by, for example, same evaluation as that performed in the initial stage changing the ratio between the flow rates of silane gas was performed. The occurrence of toner filming on the and methane gas which are introduced into the dis surface of the drum which was caused by the endurance charge space. The state of bonding of silicon atoms can 50 test was also evaluated. If required, the amount of the be arbitrarily controlled by displacing silane gas and atoms and bonding state of the atoms in the surface methane gas by tetramethylsilane gas. In addition, the layer were also analyzed by ESCA. bonding state can be more effectively controlled by A plurality of pieces were cut from portions of each changing the bias voltage applied to the discharge of the samples corresponding to the upper and lower space. The amount of the hydrogen atoms contained in 55 portions of an image portion and subjected to quantita the second layer region can be controlled according to tive analysis of the silicon, carbon, oxygen, hydrogen desire by, for example, arbitrarily changing the flow and fluorine atoms, which were contained in the layer, rate of hydrogen gas introduced into the discharge by Auger, SIMS and chemical analysis, as occasion space. demanded. If required, the amount of the atoms and the When a second layer region containing oxygen atons bonding state in the surface were also analyzed by is formed on the first layer region formed, discharge is ESCA. started by the same method as that employed for form Tables 3 and 4 show the results of the evaluation and ing the first layer region with the exception that the the initial values obtained by quantitative analysis. In composition of raw material gas introduced into the Table 4, the total content of silicon, carbon, oxygen, reactor 1101 is changed to, for example, silane gas, 65 hydrogen and fluorine atoms is 100 atomic %. It was methane gas, tetramethylsilane gas, oxygen gas, nitro found from the results that there is a proper ratio of gen monoxide gas and, if required, hydrogen gas as silicon atoms bonded to carbon atoms. The remarkable dilution gas. superiority of the drums was confirmed in the proper 5,284,730 23 24 ties after the endurance test in a high-humidity environ bonded to oxygen atoms to produce drums under the six ment. different conditions G to L, as shown in Table 6. In TABLE addition, separate surface layers only (referred to as - LayerStructure - 5 “samples' hereinafter) were formed on the same cylin Film-Forming Photoconductive Surface der by using the same apparatus as that shown in FIGS. Conditions Layer Layer 6 and 7. Raw Gas Flow Rate The drums and samples were evaluated and analyzed SiH4 300 sccm k in the same manner as those in Example 1. Si(CH3) 0 scc.n Tables 7 and 8 show the results of the evaluation and CH 0 sccm 1O the initial values obtained by quantitative analysis. In (CH3)2O 0 sccm 20 sccm O2 0 sccm 14 sccm Table 8, the total content of silicon, carbon, oxygen, NO 3 sccm 2 sccm hydrogen and fluorine atoms is 100 atomic 76. It was B2H6 50 ppm 0 ppm found from the results that there is a proper ratio of H2 800 sccm 1000 sccm SiF 0 sccm 15 scorn 15 silicon atoms bonded to oxygen atoms. The remarkable Pressure 13 mTorr 13 mTorr superiority of the drums was confirmed in the proper Microwave Power 1000 W 1000 W ties after the endurance test in a high-humidity environ Bias Voltage 70 V 70 V net. Layer Thickness 25 um 0.03 um Shown in Table 2 TABLES 2O - Layer Structure - Film-Forming Photoconductive Surface TABLE 2 Conditions Layer Layer - SampleName Raw Gas Flow Rate Raw Gas A B C D E F SiH4 350 sccrin 25 sccm SiH4 (sccm) 20 25 30 40 50 60 25 Si(CH3)4 0 sccm 70 sccrin Si(CH3)4 80 70 60 40 20 O CH4 0 sccIn 60 scom (sccm) O2 0 sccm CH4 (sccm) 30 60 90 150 20 270 NO 3 sccm B2H6 50 ppm 0 ppm H2 800 scom 1000 sccm TABLE 3 30 SiF 0 sccm 15 sccm Pressure 3 Torr 13 mTorr Sample Name Microwave Power 000 W 1000 W Evaluation Item A B C D E F Bias Voltage 70 V 70 V Initial Chargeability (c) () (6) (e) (o) (6) Layer Thickness 25 um 0.03 um Properties Sensitivity (o) (c) (o) (c) (o) (c) Show in Table 6 Image Flowing (c) (c) (C) (G) (6) (c) 35 Residual Potential GD G) (G) G) (6) (c) Ghost G) G) o c O TABLE 6 Image Defect (o) (o) (c) () (6) (e) After Chargeability (o) (o) (c) () (c) () - SampleName Endurance Sensitivity (o) (3) (o) (o) (c) (e) Raw Gas G H I J K L Test at Image Flowing (e) (6) (e) o A 40 High Residual Potential (6) (e) () () (6) (e) O2 (scCm) O 6 10 16 18 20 Humidity Ghost (o) (c) d d o NO (sccm) 40 28 20 8 4. O Image Defect o 0. d o c d Toner Filming (6) O A X X Evaluation: G . . . Very good, c. ... Good, A ... No practical difficulty. x . . . Not TABLE 7 practical. 45 Sample Name Evaluation Item G H I B K L TABLE 4 Initial Chargeability (c) (o) (o) (o) (o) (c) (e) Properties Sensitivity (6) (6) (o) (o) (o) (o) (6) Component Ratio (atomic 26) - Image Flowing (c) GD G) G O Ge) (e) Element A B C D E F Residual Potential G (o) (c) (o) (6) (e) (c) Si (total) 2.0 1.3 2.3 2.5 13. 12.8 50 Ghost o o G (o) (6) o o Si (Si-C) 1.0 8.3 7.4 6.4 5.5 3.2 Image Defect (o) (6) () (o) (6) () (6) Si (Si-O) 2.8 3.0 3. 3.2 3.0 2.8 After Chargeability (o) (c) (o) (o) (o) (o) (6) C (Total) 24.2 24.8 23.2 22.7 22. 22.0 Endurance Sensitivity (o) (O Go Go) (c) () (e) O (Total) 5.8 S.1 6.0 5.7 5.4 6.2 Test at Image Flowing o (o) (o) (o) (6) o A H 56.4 56.8 56.6 57.5 57.4 57.5 High Residual Potential GD G). G. G. G. G. G.) F 1.6 2.0 19 16 1.8 15 55 Humidity Ghost o o (o) (c) G) o (6) Si (Si-C): Component ratio of Siatons having Si-C bonding. Image Defect C. C. 0 Si (Si-O): Component ratio of Siatons having Si-O bonding. Toner Filming x A (6) (o) (c) A x Evaluation: (e)...Very good, O... Good, A... No practical difficulty, x ... Not practical, EXAMPLE 2 60 An electrophotographic light-receiving member was TABLE 8 formed by using the production apparatus shown in FIGS. 6 and 7 in accordance with the same procedure Component Ratio (atomic %) as that in Example 1. The conditions for the formation Element G H I B J K L Si (Total) 12.5 2.0 12.3 11.3 3 1.0 11.5 of a photoconductive layer and a surface layer were as 65 Si (Si-C) 9.3 8.9 8.9 8.3 9.0 8.4 8.5 shown in Table 5. In regard to the surface layer, the Si (Si-O) 5.6 4.0 3.5 3.0 1.4 0.9 0.5 flow rates of nitrogen monoxide gas and oxygen gas C (Total) 21.8 23.3 24.1 24.8 26.0 27.3 27.6 were changed for changing the ratio of silicon atoms O (Total) 7.5 6.7 5.9 5.1 S.2 4.3 4.0 5,284,730 25 26 TABLE 8-continued TABLE 1 1-continued Component Ratio (atomic %) F Content Element G H I B J K L Sample Name (atonic 26) Evaluation H 56.0 56.0 55.9 56.8 55.4 55.4 57.6 M 0.10 o-A F 2.2 2.0 1.8 2.0 2. i.8 2.3 N 0.32 O O 0.69 (6) Si(Si-C): Component ratio of Siatoms having Si-C bonding. P 3.7 O) Si (Si-O): Component ratio of Siatoms having Si-O bonding. Q 6.9 O R 9.6 o-A Comparative Example 2 11.0 X EXAMPLE 3 10 The content of fluorine atoms in the surface layer was The results of evaluation shown in Table ll show com changed within the range of the invention to prepare a parison of the number of silicon atoms bonded to carbon plurality of analytical samples under the conditions of atoms after the corona discharge with that before the film formation shown in Table 9. Each of the samples 15 corona discharge on the basis of the following criteria: was set in an electrophotographic apparatus (produced O) . . . Substantially no change by remodeling NP7750 manufactured by Canon Inc. for o . . . Slight decrease was confirmed. tests in the invention) and then subjected to corona A . . . Significant decrease was confirmed, without discharge corresponding to copying of 1,000,000 sheets any trouble in a usual use method under the condition that a voltage of 6 kV was applied 20 x . . . Significant decrease was confirmed, without to a charger. The number of silicon atoms bonded to practicability. carbon atoms after the corona discharge was compared In the table, O-A shows that when the same experi with that before the corona discharge. ment was repeated several times, both the marks o TABLE 9 and A were obtained as results of evaluation. Sample Name 25 EXAMPLE 4 Film-Forming Conditions M N O P Q R A charge injection inhibition layer, a photoconduc Raw Gas Flow Rate SCC tive layer and a lower surface layer were formed on a SiH4 34 33 30 11 0. 0 substrate by using the production apparatus shown in Si(CH3)4 70 70 70 70 70 70 30 FIGS. 6 and 7 under the conditions shown in Table 12, CH4 60 60 60 60 55 35 and a surface layer was then formed under the same O2 14 14 14 14 4. 14 NO 2 12 12 12 12 12 conditions as those for Sample A of Example 1. SiF4 1.2 3 7.5 36 52.5 52.5 TABLE 12 CF4 O O O 0 7.5 37.5 H 1000 000 1000 1000 1000 1000 35 Layer Structure Pressure (mTorr) 13 13 13 13 3 3 Charge Microwave Power (W) 1000 1000 1000 000 1000 1000 Film- Injection Photo- Lower Bias Voltage (V) 70 70 70 70 70 70 Forming Inhibition conductive Surface Layer Thickness (um) 0.03 0.03 0.03 0.03 0.03 0.03 Conditions Layer Layer Layer Raw gas flow rate 40 SiH4 350 sccm 350 sccm 70 scen COMPARATIVE EXAMPLES 1 and 2 Ne 100 sccm 100 scorn 100 sccm CH4 35 sccm 0 sccm 350 scorn For comparison with the samples prepared in Exam B2H6 1000 ppm 0 ppm 0 ppm ple 3, analytical samples were prepared under the pro Pressure 13 Torr 13 mTorr 12 mTorr Microwave Power 1000 W 1000 W 1000 W duction conditions shown in Table 10 and evaluated by 45 Bias Voltage 100 V 100 V 100 V the same method as that employed in Example 3. Layer Thickness 3 um 20 m 0.5 pm TABLE 10 Comparative Comparative As a result of evaluation of the drum in the same manner Film-Forming Conditions Example 1 Example 2 as in Example 1, good results were obtained, in accor Raw Gas Flow Rate (sccm) - 50 dance with the drum formed under the conditions for SiH4 34 O Sample A of Example 1. Si(CH3)4 70 70 CH4 60 25 EXAMPLE 5 O2 14 14 NO 12 2 A photoconductive layer was formed under the con SiF4 0.7 52.5 55 ditions shown in Table 13, and a surface layer was then CF4 O 52.5 H2 000 000 formed under the same conditions as those in Sample B Pressure (mTorr) 13 13 of Example 1. Microwave Power (W) 1000 1000 TABLE 13 Bias Voltage (V) 70 70 Layer Thickness (pm) 0.03 0.03 60 - LayerStructure Charge Filin- Injection Charge Charge The results obtained from Example 3 and Comparative Forming Inhibition Transport Generating Examples 1 and 2 are shown in Table 11. Conditions Layer Layer Layer TABLE 1 65 Raw gas flow rate SiH4 350 sccIn 350 sccm 350 sccm F Content Ne 100 sccm 100 sccIn 100 sccm Sample Name (atomic 9%) Evaluation CH4 35 sccm 35 scom 0 sccm Comparative Example l 0.08 A B2H6 1000 ppm 0 ppm 0 ppm 5,284,730 27 28 TABLE 13-continued EXAMPLE 9 Layer Structure An electrophotographic light-receiving member was Charge Fin- Injection Charge Charge formed on a planished aluminum cylinder by using the Forming Inhibition Transport Generating production apparatus shown in FIGS. 6 and 7. The Conditions Layer Layer Layer conditions for the formation of a photoconductive layer Pressure mTorr 11 Torr 10 mTorr and a surface layer were as shown in Table 15. In regard Microwave Power 1000 W 1000 W 000 W to the surface layer, the flow rates of silane gas, methane Bias Voltage 100 W 100 V 100 V gas and tetramethylsilane gas were changed for chang Layer Thickness 3 um 20 m 0.5 um 10 ing the ratio of silicon atoms bonded to carbon atoms to produce light-receiving members (referred to as As a result of evaluation of the drum in the same manner "drums' hereinafter) under the six different conditions as in Example 1, good results were obtained, in accor A to F, as shown in Table 16. In addition, separate dance with the drum formed under the conditions for surface layers only (referred to as "samples' hereinaf Sample B of Example 1. 15 ter) were formed on the same cylinder by using the . same apparatus as that shown in FIGS. 6 and 7. EXAMPLE 6 The drum was set in an electrophotographic appara tus (produced by converting NP7550 manufactured by A photoconductive layer was formed by the RF Canon Inc. for tests in the invention). The initial elec discharge process under the conditions shown in Table 20 trophotographic properties such as chargeability, sensi 14, and a surface layer was then formed by using the tivity, image flowing in high-humidity environment production apparatus shown in FIGS. 6 and 7 under the (atmospheric temperature: 31 C., humidity: 85%), re same conditions as those for Sample B of Example 1. sidual potential, ghost, image defect and the like were TABLE 14 evaluated under various conditions. The drum was then 25 Layer Structure subjected to an endurance test in which printing on Film-Forming Charge Injection Photo 500,000 sheets was performed at atmospheric tempera Conditions Inhibition Layer conductive Layer ture of 33 C. and a humidity of 90% without using Raw gas flow rate - drum heating means, such as a drum heater or the like, SiH4 250 sccm 350 sccm 30 and the same evaluation as that performed in the initial Ne 250 sccm 350 sccm stage was performed. The occurrence of toner filming CH4 0 sccIn O sccm on the surface of the drum which was caused by the B2H6 1000 ppm 0 ppm endurance test was also evaluated. If required, the Pressure 0.3 mTorr 0.5 mTorr amount of the atoms and the bonding state of the atoms RF Power 300 W 400 W in the surface layer were also analyzed by ESCA. Layer Thickness 3 um 20 um 35 A plurality of pieces were cut from portions of each of the samples corresponding to the upper and lower As a result of evaluation of the thus-formed drum in the portions of an image portion and subjected to quantita same manner as in Example l, good results were ob tive analysis of the silicon, carbon, oxygen, hydrogen tained, in accordance with the drum formed under the and fluorine atoms, which were contained in the layer, conditions for Sample B of Example 1. by Auger, SIMS and chemical analysis, as the occasion demanded. If required, the amount of the atoms and the EXAMPLE 7 bonding state in the surface were also analyzed by The same photoconductive layer as that formed in ESCA. Example 1 was formed, and a surface layer was then Tables 17 and 18 show the results of the evaluation formed under the same conditions as those for Sample B 45 and the initial values obtained by quantitative analysis. of Example l, while the thickness was changed to a In Table 18, the total content of silicon, carbon, oxygen, value from 5 A to 1 um. hydrogen and fluorine atoms is 100 atomic %. It was As a result of evaluation of the thus-formed drum in found from the results that there is a proper ratio of the same manner as in Example 1, good results were silicon atoms bonded to carbon atoms. The remarkable obtained from samples comprising the surface layers 50 superiority of the drums was confirmed in their proper having thicknesses from 10 A to 500 A, in accordance ties after the endurance test in a high-humidity environ with the drum formed under the conditions for Sample et. B of Example 1. The advantages of the present inven TABLE 1.5 tion were thus confirmed. 55 - Layer Structure EXAMPLE 8 Film-Forming Photoconductive Surface Conditions Layer Layer The same evaluations as those performed in Exam Raw Gas Flow Rate ples 1 to 7 were performed, while the contents of sili SiH4. 300 sccm con, carbon, oxygen, hydrogen and fluorine atoms in Si(CH3)4 O sccm the surface layer were changed. As a result, it was con CHA 0 sccm (CH3)2O O sccm 20 sccm firmed that assuming that the composition of a surface O O sccm 7 scorn layer is (SiC.O.).H.F (wherein x+y+z= 1, NO 3 sccm 6 scom t-i-u-v= 1), when 0.1 SxS 0.4, 0.4 Sys 0.7, B2H6 50 ppm 0 ppm 0.05s Zs. O.2, 0.299 sts 0.589, 0.41sus 0.7, and 65 H2 OO sccm 400 sccm SiF4 O sccin 15 scorn 0.001 s vs 0.1, the drum of the present invention shows Pressure 8 mTorr 9 mTorr good electrophotographic properties. The advantages Microwave Power 1000 W 900 W of the present invention were thus confirmed. Bias Voltage OO V 120 V 5,284,730 29 30 TABLE 15-continued found from the results that there is a proper ratio of Layer Structure silicon atoms bonded to oxygen atoms. The remarkable Film-Forming Photoconductive Surface superiority of the drums was confirmed in the proper Conditions Layer Layer ties after the endurance test in a high-humidity environ Layer Thickness 25 um 0.03 um nent. Shown in Table 16 TABLE 19 - LayerStructure TABLE 16 Film-Forming Photoconductive Surface Conditions Layer Layer Sample Name 10 Raw Gas A. B C D E F Raw Gas Flow Rate SiH4 350 scc.n 25 sccm SiH4 (sccm) 20 2S 30 40 50 60 Si(CH3)4 O sccm 70 scc. Si(CH3)4 (scom) 80 70 60 40 20 O CH4 0 sccm 30 sccm CH4 (scCm) 0 30 60 120 180 240 (CH3)2O 0 sccm 20 sccm 15 O2 0 sccm NO 3 sccm g TABLE 17 B2H6 50 ppm 0 ppm H2 100 sccm 400 ppm Sample Name SiF4 0 scc.n 15 scc.n Evaluation. Item A B C D E F Pressure 8 norr 9 in Torr Initial Chargeability G) (o) (6) () (O G) 2O Microwave Power 1000 W 900 W Properties Sensitivity (o) (o) (o) (c) (o) (c) Bias Voltage 100 V 120 V Image Flowing O) (C) (o) (c) (o) (c) Layer Thickness 25 um 0.03 um Residual Potential G. G. G. G. G) (6) Shown in Table 20 Ghost (o) (o) o o o O Image Defect (o) (c) (o) (o) (o) (O) After Chargeability O (o) (6) (e) (c) (e) 2 5 TABLE 20 Endurance Sensitivity O Go) (e) (e) Go) (c) Test at Image Flowing G) (c) () o o A Sample Name High Residual Potential G) (G) G) () (6) (c) Raw Gas G H I J K L Humidity Ghost G G) o o o C O2 (sccm) O 3 5 8 9 10 Image Defect d O O d d d NO (sccm) 20 4. O 4. 2 O Toner Filming G) (c) o A X X 3 O Evaluation; (c) . . . Very good, c. . . Good, A... No practical difficulty, x . . . Not practical. TABLE 21 TABLE 1.8 Sample Name Evaluation item G H I B J K L Component Ratio (atomic %) 35 Initial Chargeability (o) (c) (o) (c) (C) (o) (c) Element A B C D E F Properties Sensitivity (e) () (6) () (o) (o) (c) Si (Total) 13.0 12.5 12.1 12.7 2.0 11.9 Image Flowing G) (o) (6) (c) (o) (c) (e) Si (Si-C) 12.0 9.0 7.3 6.6 5.1 3.0 Residual Potential G. G. G. G. G. (e) G) Si (Si-O) 2.6 2.7 3.2 2.9 2.8 3. Ghost o o G) G) (G) c o C (Total) 25.1 24.0 23.7 25.1 22.1 21.8 Image Defect GD G) (O Ge (e) (c) (c) C (C-O) 5. 4.2 5.3 4.7 4.8 5. 40 After Chargeability O) () (o) (o) (o) (o) (6) O (Total) 6.1 5.3 7.0 5.8 6.2 5.5 Endurance Sensitivity (o) (o) (6) (e) (e) (c) (e) H 54.0 56.3 55.2 54.7 57.9 59. Test at Image Flowing o G) (G) G) (C) O A F 1.8 1.9 2.0 1.7 18 1.7 High Residual Potential G) (c) (o) (G) G) (o) (c) Si (Si-C): Component ratio of Si atoms having Si-C bonding. Humidity Ghost o o (o) (6) (O o (o) Si (Si-O): Component ratio of Siatons having Si-O bonding. Image Defect c O d d o o o C (C-O): Component ratio of C atoms having C-O bonding. 45 Toner Filming x A (o) (O G) A X Evaluation; (e)... Very good, c. . . Good, A... No practical difficulty, x . . . Not practical. EXAMPLE 10 An electrophotographic light-receiving member was TABLE 22 formed by using the production apparatus shown in 50 FIGS. 6 and 7 in accordance with the same procedure Component Ratio (atomic 26) as that in Example 9. The conditions for the formation Element G H B J K L of a photoconductive layer and a surface layer were as Si (Total) 12.4 12.3 2.0 12.5 11.9 11.7 11.3 Si (Si-C) 9. 8.9 9.2 9.0 8.7 9.1 8.4 shown in Table 19. In regard to the surface layer, the Si (Si-O) 5.4 3.9 3.4 2.7 1.3 0.9 0.5 flow rates of nitrogen monoxide gas and oxygen gas 55 C (Total) 23.0 24.1 23.9 24.0 25.0 26.9 27.1 were changed for changing the ratio of silicon atoms C (C-O) 5.1 4.9 4.7 4.2 S.2 4.8 5.1 bonded to oxygen atoms to produce drums under the six O (Total) 6.3 5.9 5.5 5.3 S. 4.9 5.0 H 56.3 55.8 56.5 56.3 56.2 54.3 54.5 different conditions G to L, as shown in Table 20. In F 2.0 1.9 2.1 1.9 1.8 2.2 2.1 addition, separate surface layers only (referred to as Si (Si-C); Component ratio of Siatoms having Si-C bonding. "samples' hereinafter) were formed on the same cylin Si (Si-O): Component ratio of Siatoms having Si-O bonding. der by using the same apparatus as that shown in FIGS. C (C-O): Component ratio of C atoms having C-O bonding. 6 and 7. The drums and samples were evaluated and analyzed in the same manner as that in Example 9. EXAMPLE 1 Tables 2i and 22 show the results of the evaluation 65 An electrophotographic light-receiving member was and the initial values obtained by quantitative analysis. formed by using the production apparatus shown in In Table 22, the total content of silicon, carbon, oxygen, FIGS. 6 and 7 in accordance with the same procedure hydrogen and fluorine atoms is 100 atomic 9%. It was as that in Example 9. The conditions for the formation 5,284,730 31 of a photoconductive layer and a surface layer were as TABLE 26 shown in Table 23. In regard to the surface layer, the flow rates of methane gas, oxygen gas, nitrogen monox Component Ratio (atomic %) ide gas and methyl ether gas were changed for changing Element M N O B P Q R Si (Total) 2.3 1.8 12.1 12.5 11.5 12. 12.3 the ratio of carbon atoms bonded to oxygen atoms to Si (Si-C) 8.8 9.1 9.0 9.0 8.5 8.7 8.8 produce drums under the six different conditions M to Si (Si-O) 2.7 2.5 2.7 2.7 2.8 3.1 2.5 R, as shown in Table 24. In addition, separate surface C (Total) 24.1 25.1 24.8 24.0 25.1 24.7 24.5 C (C-O) 10.8 8.5 6.9 4.2 2.9 1.6 .3 layers only (referred to as "samples' hereinafter) were O (Total) 7.2 6.2 5.8 5.3 S.4 5.1 4.8 formed on the same cylinder by using the same appara 10 H 54.4 54.8 55.1 56.3 56.2 56.0 56.7 tus as that shown in FIGS. 6 and 7. F 2.0 2. 2.2 19 1.8 2. 1.7 The drums and samples were evaluated and analyzed Si (Si-C); Component ratio of Si atoms having Si-C bonding. in the same manner as that in Example 9. Si (Si-O): component ratio of Si atoms having Si-O bonding. Tables 25 and 26 show the results of the evaluation C (C-o): Component ratio of C atoms having C-O bonding. and the initial values obtained by quantitative analysis. 15 It was found from the results that there is a proper ratio EXAMPLE 12 of carbon atoms bonded to oxygen atoms. The remark The content of fluorine atoms in the surface layer was able superiority of the drums was confirmed in the changed within the range of the invention to prepare a properties after the endurance test in a high-humidity plurality of analytical samples under the conditions of environment. 20 film formation shown in Table 27. Each of the samples TABLE 23 was set in an electrophotographic apparatus (produced Layer Structure by converting NP7750 manufactured by Canon Inc. for Film-Forming Photoconductive Surface tests in the invention) and then subjected to corona Conditions Layer Layer 25 discharge corresponding to copying of 1,000,000 sheets under the condition that a voltage of 6 kV was applied Raw Gas Flow Rate to a charger. The number of silicon atoms bonded to SiH4 350 scc.n 25 sccm Si(CH3)4 0 sccm 70 sccm carbon atoms after the corona discharge was compared CH4 0 sccm with that before the corona discharge. (CH3)2O 0 sccm 30 TABLE 27 O2 0 sccm k NO 3 sccm k Sample Nane B2H6 50 ppm 0 ppm Film-Forming Conditions S T U V W X H2 100 sccm 400 sccIn Raw Gas Flow Rate SiF4 0 scom 15 sccm (son)- Pressure 8 Torr 9 mTorr 35 SiH4 34 33 30 O O Microwave Power 1000 W 900 W Si(CH3)4 70 70 70 70 70 70 Bias Voltage 100 V 120 V CH4 30 30 30 30 25 5 Layer Thickness 25 um 0.03 um (CH3)2O 20 20 20 20 20 20 Shown in Table 24 O2 7 7 7 7 7 7 40 NO 6 6 6 6 6 6 SiF4 1.2 3 7.5 36 52.5 52.5 TABLE 24 CF4 O O O 0 7.5 37.5 H2 400 400 400 400 400 400 - SampleName - Pressure (mTorr) 9 9 9 9 9 9 Raw Gas M N O P Q R Microwave Power (W) 900 900 900 900 900 900 CH4 (scom) O 10 20 40 50 60 45 Bias Voltage (V) 120 120 120 120 120 120 (CH3)2O 40 33 26 14 7 O Layer Thickness (Lm) 0.03 0.03 0.03 0.03 0.03 0.03 (sccm) O2 (sccm) O 3 5 9 14 NO (scCm) 0 2 4. 8 10 12 COMPARATIVE EXAMPLES 3 AND 4 50 For comparison with the sample prepared in Exam TABLE 25 ple 12, analytical samples were prepared under the pro Sample Name duction conditions shown in Table 28 and evaluated by Evaluation Item M. N. O. B P Q R the same method as that employed in Example 12. Initial Chargeability (c) (o) (o) (c) () (c) (o) 55 TABLE 28 Properties Sensitivity (c) (o) (6) (c) (o) (o) (6) - Comparative Comparative Image Flowing (o) (o) (c) (c) (o) (o) (6) Film-Forming Conditions Example 3 Example 4 Residual Potential G) () (6) (o) (c) () (e) Ghost o o G) (G) () o o Raw Gas Flow Rate (sccm) Image Defect (o) (c) () (o) (o) (o) (c) SiH4 34 O Si(CH3)4 70 70 After Chargeability (c) (o) (c) (o) (o) (o) (c) 60 CH4 30 O Endurance Sensitivity (o) (o) (c) (o) (o) (o) (O) (CH3)2O 20 20 Test at Image Flowing o (o) G (6) (O) o A O2 7 7 High Residual Potential (o) (o) (c) (o) (c) () (e) NO 6 6 Humidity Ghost o o G) G) G) o G) SiF4 0.7 52.5 Image Defect O O. O C O O C. CF4 0 52.5 Toner Filming x A (o) (e) (c) A x 65 H2 400 400 Evaluation; (6) ... Very good, o, ... Good, A... No practical difficulty, x ... Not Pressure (mTorr) 9 9 practical. Microwave Power (W) 900 900 Bias Voltage (V) 120 120 5,284,730 33 34 TABLE 28-continued TABLE 31 Comparative Comparative - Layer Structure Film-Forming Conditions Example 3 Example 4 Charge Film- Injection Charge Charge Layer Thickness (um) 0.03 0.03 5 Forming Inhibition Transport Generating Conditions Layer Layer Layer The results obtained from Example 12 and Compara Raw Gas Flow Rate tive Examples 3 and 4 are shown in Table 29. SiH4 350 sccm 350 scom 350 scCm Ne 100 sccm 100 scom 100 sccm TABLE 29 10 CH4 35 sccm 35 scom 0 sccIn F Content B2H6 1000 ppm 0 ppm 0 ppm Sample Name (atomic %) Evaluation Pressure 10 Torr 10 Torr 9 mTorr Microwave Power 1000 W 1000 W 1000 W Comparative Example 3 0.08 A Bias Voltage 100 V 100 V 100 V S 0.11 o-A Layer Thickness 3 um 20 um 0.5 m T 0.31 O U 0.68 O 15 V 3.7 O) As a result of evaluation of the drum in the same manner W 6.5 d as in Example 9 good results were obtained, in accor X 9.5 o-A dance with the drum formed under the conditions for Comparative Example 4 10.8 X Sample B of Example 9. 20 The results of evaluation shown in Table 29 show EXAMPLE 1.5 comparison of the number of silicon atoms bonded to A photoconductive layer was formed by the RF carbon atoms after the corona discharge with that be discharge process under the conditions shown in Table fore the corona discharge on the basis of the following 32 and a surface layer was then formed by using the criteria: 25 production apparatus shown in FIGS. 6 and 7 under the O) . . . Substantially no change. same conditions as those for Sample B of Example 9. o . . . Slight decrease was confirmed. A . . . Significant decrease was confirmed, without TABLE 32 any trouble in a conventional method. Layer Structure x . . . Significant decrease was confirmed, without 30 Film-Forming Charge Injection Photo practicability. Conditions Inhibition Layer conductive Layer Raw Gas Flow Rate In the table, O-A shows that when the same experi SiH4 250 scom 350 sccm ment was repeated several times, both the marks o and Ne 250 sccm 350 sccm A were obtained as results of evaluation. CH4 0 sccm 0 sccm 35 B2H6 1000 ppm 0 ppm EXAMPLE 13 Pressure 0.3 mTorr 0.5 Torr RF Power 300 W 400 W A charge injection inhibition layer, a photoconduc Layer Thickness 3 um 25 um tive layer and a lower surface layer were formed on a substrate by using the production apparatus shown in As a result of evaluation of the thus-formed drum in the FIGS. 6 and 7 under the conditions shown in Table 30, 0 same manner as in Example 9, good results were ob and a surface layer was then formed under the same tained, in accordance with the drum formed under the conditions as those for Sample A of Example 9. conditions for Sample B of Example 9. TABLE 30 - Layer Structure - EXAMPLE 16 Charge The same photoconductive layer as that formed in Film. Injection Photo- Lower Example 9 was formed, and a surface layer was then Forming Inhibition conductive Surface formed under the same conditions as those for Sample B Conditions Layer Layer Layer of Example 9, while the thickness was changed to 5 A Raw Gas Flow Rate 50 to 1 um. SiH4 350 sccm 350 scc.n 70 sccIn As a result of evaluation of the thus-formed drum in Ne 100 sccm 100 scom 100 scom CH4 35 sccIn 0 sccIn 350 scc.n the same manner as in Example 9, good results were B2H6 1000 ppm 0 ppm 0 ppm obtained from samples comprising the surface layers Pressure 10 mTorr 9 mTorr 1 InTorr having thicknesses from 10 A to 500 A, like the drum Microwave Power 1000 W 1000 W 1000 W 55 formed under the conditions for Sample B of Example Bias Voltage 100 V 100 V 100 V 9. The advantages of the present invention were thus Layer Thickness 3 in 20 um 0.5 um confirmed. As a result of evaluation of the drum in the same manner EXAMPLE 17 as in Example 9, good results were obtained, in accor The same evaluations as those performed in Exam dance with the drum formed under the conditions for ples 9 to 15 were performed, while the contents of sili Sample A of Example 9. con, carbon, oxygen, hydrogen and fluorine atoms in the surface layer were changed. As a result, it was con EXAMPLE 14 firmed that assuming that the composition of a surface A photoconductive layer was formed under the con 65 layer is (SiCO).H.Fy (wherein x+y+z=1, ditions shown in Table 31, and a surface layer was then t- u + v = 1), when 0.1 SxS 0.4, 0.4Sys 0.7, formed under the same conditions as those in Sample B 0.05szs 0.2, 0.299 sts 0.589, 0.41sus 0.7, and of Example 9. 0.001 s vs 0.1, the drum of the present invention shows 5,284,730 35 36 good electrophotographic properties. The advantages 0.299 sts 0.589, 0.41sus 0.7, 0.001 Svs 0.1 and of the present invention were thus confirmed. t-- u + v = 1. The electrophotographic light-receiving member of 2. An electrophotographic light-receiving member the present invention which is designed so as to have according to claim 1, wherein the thickness of said the above-described layer structure is capable of solving non-single crystal layer is 10 to 500 A. all the problems and exhibits excellent electrical, optical 3. An electrophotographic light-receiving member, and photoconductive properties and excellent durabil comprising a non-single crystal layer comprising at least ity and working environmental properties. silicon, carbon, oxygen, hydrogen and fluorine atoms as The present invention can also provide an electro an outermost surface, wherein the ratio of silicon atoms photographic light-receiving member excellent in pre bonded to carbon atoms in said non single crystal layer venting filming. is 50 to 100 atomic 26 of the total number of silicon Particularly, the present invention enables the attain atoms therein, the ratio of silicon atoms bonded to oxy ment of a great effect of preventing filming of a toner gen atoms is 10 to 30 atomic % of the total number of for pressure fixing. silicon atoms therein, the ratio of carbon atoms bonded While the present invention has been described with 15 to oxygen atoms is 10 to 30 atomic 76 of the total num respect to what is presently considered to be the pre ber of carbon atoms therein and said non-single crystal ferred embodiments, it is to be understood that the in layer is substantially composed of non-single crystal vention is not limited to the disclosed embodiments. To silicon having the formula (SiC.O.).H.F wherein the contrary, the invention is intended to cover various 0.1 SxS0.4, 0.4sys0.7, 0.05sz S0.2, modifications and equivalent formulations included 20 0.299 sts 0.589, 041sus O.7, 0.001 s vs 0.1, within the spirit and scope of the appended claims. The X--y-Z = 1 and t-u-v= 1. scope of the following claims is to be accorded the 4. An electrophotographic light-receiving member broadest interpretation so as to encompass all such mod according to claim 3, wherein the thickness of said ifications and equivalent formulations and functions. non-single crystal layer is 10 to 500 A. What is claimed is: 25 5. An electrophotographic light-receiving member 1. An electrophotgraphic light-receiving member according to any one of claims 1 or 3, wherein the ratio comprising a non single crystal layer comprising at least of silicon atoms bonded to carbon atoms in said outer silicon, carbon, oxygen, hydrogen and fluorine atoms as most surface layer is at least 60% of the total number of an outermost surface layer, wherein the ratio of silicon silicon atoms in said outermost surface layer. atoms bonded to carbon atoms in said non-single crystal 30 6. An electrophotographic light-receiving member layer is 50 to 100 atomic 9% of the total number of silicon according to claim 5, wherein said ratio is at least 70%. atoms therein, the ratio of silicon atoms bonded to oxy 7. An electrophotographic light-receiving member gen atoms in said non-single crystal layer is 10 to 30 according to any one of claims 1 or 3, wherein the atomic 76 of the total number of silicon atoms therein, content of carbon atoms in said surface layer is 40 to 90 and said non-single crystal layer is substantially com 35 atomic % of the total number of silicon and carbon posed of a non-single crystal (SiC.O.).H.F wherein atoms in said outermost surface layer. 0.1 SxS 0.4, 0.4sys 0.7, 0.05s zs 0.2, x + y +z= 1, k

45

SO

55

65 - UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5,284,730 DATED February 8, 1994 NVENTOR(S) : TETSUYA TAKEI Err ar. Page 1 of 3 it is certified that error appears in the above-identified patent and that said Letters Patant is hereby Corrected as shown below:

ON TITLE PAGE In 56 References Cited, under FOREIGN PATENT DOCUMENTS: "60-67951 4/1984 Japan" should read --60-67951 4/1985 Japan--. COLUMN 3 Line 6, "O3stsO. 59, " should read --O.35tsO. 59, --. COLUMN 5 Line 39, "cased" should read --caused.--. Line 43, "surface" should read --surface of.--. COLUMN 6 Line 16, "portion" should read --portions--. Line .34, "SiO," should read --SiO, --. COLUMN 10 Line 25, "radius R," should read --radius R' --. COLUMN 11. Line 9, "(3) n-containing" should read -- (3) n-type A-Si(H,X)-containing--. Line 43, "SiH," should read --SiH, SiH,--.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 5,284,730 OATED ; February 8, 1994 NVENTOR(S) : TETSUYA TAKEI, ET AL. Page 2 of 3 It is certified that error appears in the above-identified patent and that said letters Patent is hereby corrected as shown below:

Line 43, "SiHRr" should read --SiHBr--.

Line 24, "a" should read - -as--.

Line 26, "Its" should read --It--.

Line 42, "know" should read --known---

"It" should read --If--. "are" should read --is--.

"hodl." should read --hold--.

"electrophotgraphic" should read --electrophotographic--. "non single" should read --non-single--. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5,284,730 OATED February 8, 1994 INVENTOR(S) : TETSUYA TAKEI. ET AL. Page 3 of 3 It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

COLUMN 36 Line 10 "non single" should read --non-single Line 20, "O4lsus.O. 7," should read --O. 4lsuso. 7, --.

Signed and Sealed this First Day of November, 1994

BRUCELEBMAN Attesting Officer Commissioner of Patents and Trademarks