Electrophotographic imaging member

Abstract: An electrophotographic imaging member having an imaging surface adapted to accept a negative electrical charge. The imaging member comprises a metal ground plane layer (8) comprising at least 50 per cent by weight of zirconium, a hole blocking layer (4), a charge generation layer (6) comprising photoconductive particles dispersed in a film forming resin binder, and a hole transport layer (7). The hole transport layer is substantially non-­ absorbing in the spectral region at which the charge generation layer generates and injects photogenerated holes but is capable of supporting the injection of photogenerated holes from the charge generation layer and transporting the holes through the charge transport layer.

Description: This invention relates in general to electrophotography and more specifically, to an electrophotographic imaging member. In the art of electrophotography an electrophotographic plate comprising a photoconductive insulating layer on a conductive layer is imaged by first uniformly electrostatically charging the surface of the photoconductive insulating layer. The plate is then exposed to a pattern of activating electromagnetic radiation such as light, which selectively dissipates the charge in the illuminated areas of the photoconductive insulating layer while leaving behind an electrostatic latent image in the non-illuminated areas. This electrostatic latent image may then be developed to form a visible image by depositing finely divided electroscopic toner particles on the surface of the photoconductive insulating layer. The resulting visible toner image can be transferred to a suitable receiving member such as paper. This imaging process may be repeated many times with reusable photoconductive insulating layers. As more advanced, higher speed electrophotographic copiers, duplicators and printers were developed, degradation of image quality was encountered during extended cycling. Moreover, complex, highly sophisticated, duplicating and printing systems operating at very high speeds have placed stringent requirements including narrow operating limits on photoreceptors. For example, the ground plane of many modern photoconductive imaging members must be highly flexible, adhere well to flexible supporting substrates, and exhibit predictable electrical characteristics within narrow operating limits to provide excellent toner images over many thousands of cycles. One type of ground plane which is gaining increasing popularity for belt type photoreceptors is vacuum deposited aluminum coated with two electrically operative layers, including a charge generating layer and a charge transport layer. However, aluminium films are relatively soft and exhibit poor scratch resistance during photoreceptor fabrication processing. In addition, vacuum deposited aluminium exhibits poor optical transmission stability after extended cycling in xerographic imaging systems. This poor optical transmission stability is the result of oxidation of the aluminium ground plane as electric current is passed across the junction between the metal and photoreceptor. The optical transmission degradation is continuous and, for systems utilizing erase lamps on the nonimaging side of the photoconductive web, has necessitated erase intensity adjustment every 20,000 copies over the life of the photoreceptor. Further, the electrical cyclic stability of an aluminum ground plane in multilayer structured photoreceptors has been found to be unstable when cycled thousands of times. The oxides of aluminum which naturally form on the aluminum metal employed as an electrical blocking layer prevent charge injection during charging of the photoconductive device. If the resistivity of this blocking layer becomes too great, a residual potential will build across the layer as the device is cycled. Since the thickness of the oxide layer on an aluminum ground plane is not stable, the electrical performance characteristics of a composite photoreceptor undergoes changes during electrophotographic cycling. Also, the storage life of many composite photoreceptors utilizing an aluminum ground plane can be as brief as one day at high temperatures and humidity due to accelerated oxidation of the metal. The accelerated oxidation of the metal ground plane increases optical transmission, causes copy quality non-uniformity and can ultimately result in loss of electrical grounding capability. After long-term use in an electrophotographic copying machine, multilayered photoreceptors utilizing the aluminum ground plane have been observed to exhibit a dramatic dark development potential change between the first cycle and second cycle of the machine due to cyclic instability, referred to as "cycle 1 to 2 dark development potential variation". The magnitude of this effect is dependent upon cyclic age and relatively humidity but may be as large as 350 volts after 50,000 electrical cycles. This effect is related to interaction of the ground plane and photoconductive materials. Another serious effect of the aluminum ground plane is the loss of image potential with cycling at low relative humidity. This cycle down voltage is most severe at relative humidities below about 10 percent. With continued cycling, the image potential decreases to a degree where the photoreceptor cannot provide a satisfactory image in the low humidity atmosphere. In Japanese Patent Publication J5 6024-356 to Fuji Photo Film KK, published March 7, 1981, an electrophotographic photoreceptor is described comprising a conductive support, an inorganic amorphous silicon photosensitive layer which produces a charge carrier by photoirradiation, and a charge blocking layer between the conductive support and the inorganic amorphous silicon photosensitive layer, the charge blocking layer forming a barrier against electric charge carriers. The charge blocking layer comprises an insulating or semiconductive material such as SiO₂, Al₂O₃, ZrO₂, TiO₂ or an organic polymer such as polycarbonate, polyvinylbutyral, etc. These charge blocking layer materials are intended to block electrons into the inorganic amorphous silicon photosensitive layer. Although not disclosed in this Japanese Patent Publication, it should be noted that charge blocking layer materials suitable for blocking electrons into an inorganic amorphous silicon photosensitive layer may not necessarily be suitable for blocking holes into an organic hole generator layer. To be operable, these blocking layers must not block holes from the positively charged inorganic amorphous silicon photosensitive layer to the conductive support. For example, an Al₂O₃ film having a thickness of several hundred angstroms utilized as a blocking layer caused dark development potential cycle down, with accompanying dark decay, of a negatively charged multilayer structured photoreceptor comprising conductive ground plane, blocking layer, charge generating layer and a hole transport layer. In some multilayered photoreceptors, the ground plane is titanium coated on a polyester film. The titanium coating is sputtered on the polyester film in a layer about 17.5 nm (175 angstroms) thick. The titanium layer acts as a conductive path for electrons during the exposure step in the photoconductive process and overcomes many of the problems presented by aluminum ground planes. Photoreceptors containing titanium ground planes are described, for example, in US-A-4,588,667. Although excellent toner images may be obtained with multilayered photoreceptors having a titanium ground plane, it has been found that charge deficient spots form in photoreceptors containing titanium ground planes, particularly under the high electrical fields employed in high speed electrophotographic copiers, duplicators and printers. Moreover, the growth rate in number and size of newly created charge deficient spots and growth rate in size of preexisting charge deficient spots for photoreceptors containing titanium ground planes are unpredictable from one batch to the next under what appear to be controlled, substantially identical fabrication conditions. Charge deficient spots are small unexposed areas on a photoreceptor that fail to retain an electrostatic charge. These charge deficient spots become visible to the naked eye after development with toner material. On copies prepared by depositing black toner material on white paper, the spots may be white or black depending upon whether a positive or reversal image development process is employed. In positive image development, charge deficient spots appear as white spots in the solid image areas of the final xerographic print. In other words, the image areas on the photoreceptor corresponding to the white spot fails to attract toner particles in positive right reading image development. In reversal image development, black spots appear in background areas of the final xerographic copy. Thus, for black spots to form, the charge deficient spots residing in background areas on the photoreceptor attract toner particles during reversal image development. The white spots and black spots always appear in the same location of the final electrophotographic copies during cycling of the photoreceptor. The white spots and black spots do not exhibit any single characteristic shape, are small in size, and are visible to the naked eye. Generally, these visible spots caused by charge deficient spots have an average size of less than about 200 micrometers. These spots grow in size and total number during xerographic cycling and become more objectionable with cycling. Thus, for example tiny spots that are barely visible to the naked eye can grow to a size of about 150 micrometers. Other spots may be as large as 150 micrometers with fresh photoreceptors. Visual examination of the areas on the surface of the photoreceptor which correspond to the location of white spots and black spots reveals no differences in appearance from other acceptable areas of the photoreceptor. There is no known test to detect a charge deficient spot other than by forming a toner image to detect the defect. US-A-4,461,819 discloses various electrophotographic imaging members including one comprising, for example, a substrate, a ground plane layer comprising Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt and the like, and an amorphous silicon charge generating layer and a charge transport layer. A barrier layer is preferred to prevent injection of carriers from the substrate where the charge generating binder layer or the charge transport layer has a free surface that is charged. Representative barrier layers are MgF₂, Al₂O₃, SiO, SiO₂ and the like insulating inorganic compounds, polyethylene, polycarbonates, polyurethanes, poly-paraxylylene and the like insulating compounds, and Au, Ir, Pt, Rh, Pd, Mo and the like metals This electrophotographic imaging member is charged with a positive charge in most of the working examples. However, a negative charge is applied in Examples 8,9,14,17,18,19, and 20. Japanese Patent Publication J5 6024-356 to Fuji Photo Film KK, published March 7, 1981 discloses an electrophotographic photoreceptor comprising a conductive support, an inorganic amorphous silicon photosensitive layer which produces a charge carrier by photoirradiation, and a charge blocking layer between the conductive support and the inorganic amorphous silicon photosensitive layer, the charge blocking layer forming a barrier against electric charge carriers. The charge blocking layer comprises an insulating or semiconductive material such as SiO₂, Al₂O₃, ZrO₂, TiO₂ or an organic polymer such as polycarbonate, polyvinylbutyral, etc. These charge blocking layer materials are intended to block electrons into the inorganic amorphous silicon photosensitive layer. US-A-4,588,667 discloses an electrophotographic imaging member comprising a substrate, a ground plane layer comprising a titanium metal layer contiguous to the substrate, a charge blocking layer contiguous to the titanium layer, a charge generating binder layer and a charge transport layer. US-A-4,439,507 discloses an electrophotographic imaging member comprising a substrate, a conductive layer, a photogenerating layer comprising certain resinous material, and a charge transport layer comprising a resinous binder and an electrically active diamine material. The conductive layer includes, for example, aluminum, nickel, brass, gold, titanium, stainless steel, chromium, graphite and the like. In an alternative embodiment, a dielectric layer may optionally be positioned between the photogenerating layer and the aluminum layer. The dielectric layer may include, for example, Al₂O₃, silicon oxides, silicon nitrides, titanates and the like. US-A-4,582,772 discloses an electrophotographic imaging member comprising a substrate, a transmissive semi-conductive layer selected from the group consisting of indium-tin oxide, cadmium tin oxide, tin oxide, titanium oxides, titanium nitrides, titanium silicides, and mixtures thereof, a photogenerating layer and a charge transport layer, comprising, for example, an electrically active diamine material. US-A-4,464,450 discloses an electrophotographic imaging member comprising a metal oxide layer, a siloxane film, a photogenerating layer and a charge transport layer, comprising, for example, an electrically active diamine material. US-A-4,587,189 discloses an electrophotographic imaging member comprising a semiconductive or conductive layer, a photogenerating layer comprising a perylene pigment, and an aryl amine hole transport layer. Japanese Patent Publication 59-212844 to Kiyousera K. K., published December 1, 1983 - An electrophotographic sensitive body is disclosed comprising an aluminum substrate and an amorphous silicon layer having reduced amounts of Fe and/or Mn "To eliminate white spots lack of density and to enhance potential acceptance...". Many metals or other materials which are highly oxidatively stable, form a low energy injection barrier to the photoconductive material when utilized as a ground plane in a photoconductive device. A hole blocking layer will not form on these oxidatively stable layers thus rendering these devices non-functional as photoconductive devices. Other metals exhibit other deficiencies of one kind or another. Prior claims to good blocking layers refer to the average performance and do not take into account the fact that there localized areas of charge injection may be present. Thus, there is a continuing need for photoreceptors having ground planes that provide improved resistance to the formation and growth of charge deficient spots. According to the present invention there is provided an electrophotographic imaging member having an imaging surface adapted to accept a negative electrical charge, the electrophotographic imaging member comprising a substrate, a metal ground plane layer applied to the substrate, a hole blocking layer, a charge generation layer comprising photoconductive particles dispersed in a film forming resin binder, and a hole transport layer, the hole transport layer being substantially non-absorbing in the spectral region at which the charge generation layer generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from the charge generation layer and transporting the holes through the charge transport layer; the imaging member being characterized in that the metal ground plane layer comprises at least 50 per cent by weight zirconium. An electrophotographic imaging member in accordance with the invention has the advantage that it stabilizes or reduces the size and number of charge deficient spots prior to cycling; greater resistance to the formation of charge deficient spots during cycling; and improved resistance to the growth in size of such spots during cycling. Also, it maintains optical transmission with cycling. A photoconductive imaging member of this invention may be prepared by providing a substrate in a vacuum, sputtering a layer of zirconium metal on the substrate in the absence of oxygen to deposit a continuous zirconium metal ground plane layer, exposing the zirconium metal ground plane layer to ambient conditions, applying a hole blocking layer on the zirconium metal layer, applying a charge generation binder layer on the blocking layer and applying a hole transfer layer on the charge generation layer. An adhesive layer may optionally be applied between the hole blocking layer and charge generation layer. The zirconium layer may be formed by any suitable coating technique, such as a vacuum depositing technique. Typical vacuum depositing techniques include sputtering, magnetron sputtering, RF sputtering, and the like. Magnetron sputtering of zirconium onto a metallized substrate can be effected by a conventional type sputtering module under vacuum conditions in an inert atmosphere such as argon, neon, or nitrogen using a high purity zirconium target. The vacuum conditions are not particularly critical. In general, a continuous zirconium film can be attained on a suitable substrate, e.g. a polyester web substrate such as Mylar available from E.I. du Pont de Nemours & Co. with magnetron sputtering. It should be understood that vacuum deposition conditions may all be varied in order to obtain the desired zirconium thickness. Typical RF sputtering systems such as a modified Materials Research Corporation Model 8620 Sputtering Module on a Welch 3102 Turbomolecular Pump is described in US-A-3,926,762. That patent also describes sputtering a thin layer of trigonal selenium onto a substrate which may consist of titanium. Instead of sputtering a thin layer of trigonal selenium onto the titanium substrate, one may sputter a thin layer of zirconium onto the titanium substrate. Another technique for depositing zirconium by sputtering involves the use of planar magnetron cathodes in a vacuum chamber. A zirconium metal target plate may be placed on a planar magnetron cathode and the substrate to be coated can be transported over the zirconium target plate. The cathode and target plate are preferably horizontally positioned perpendicular to the path of substrate travel to ensure that the deposition of target material across the width of the substrate is of uniform thickness. If desired, a plurality of targets and planar magnetron cathodes may be employed to increase throughput, coverage or vary layer composition. Generally, the vacuum chamber is sealed and the ambient atmosphere is evacuated to about 658 x 10⁻⁶Pa (5 x 10⁻⁶ mm Hg). This step is immediately followed by flushing the entire chamber with argon at a partial pressure of about 131.6 x 10⁻³Pa (1 x 10⁻³ mm Hg) to remove most residual wall gas impurities. An atmosphere of argon at about 131.6 x 10⁻⁴Pa (1 x 10⁻⁴ mm Hg) is introduced into the vacuum chamber in the region of sputtering. Electrical power is then applied to the planar magnetron and translation of the substrate at approximately 3 to about 8 meters per minute is commenced. If desired, an alloy of zirconium with a suitable metal such as niobium, tantalum, vanadium and hafnium, titanium, nickel, stainless steel, chromium, tungsten, molybdenum, and the like, and mixtures thereof may be substituted for the zirconium target to deposit a layer comprising a mixture of the evaporated metals. The target may be made of a pressed mixture of the metal powders where alloy combinations may be difficult to achieve. The selected combinations of metal powders are measured, weighed, and thoroughly mixed and compressed to form a sputtering target. The conductive layer may, in another embodiment of this invention, comprise a plurality of metal layers with the outermost metal layer (i.e. the layer closest to the generator layer) comprising at least 50 percent by weight of zirconium. At least 70 percent by weight of zirconium is preferred in the outermost metal layer for even better results. The multiple layers may, for example, all be vacuum deposited or a thin layer can be vacuum deposited over a thick layer prepared by a different techniques such as by casting. Typical metals that may be combined with zirconium include titanium, niobium, tantalum, vanadium, hafnium, and the like, and mixtures thereof. Thus, as an illustration, a zirconium metal layer may be formed in a separate apparatus than that used for previously depositing a titanium metal layer or multiple layers can be deposited in the same apparatus with suitable partitions between the chamber utilized for depositing the titanium layer and the chamber utilized for depositing zirconium layer. The titanium layer may be deposited immediately prior to the deposition of the zirconium metal layer. Ground planes comprising zirconium tend to continuously oxidize during xerographic cycling due to anodizing caused by the passage of electric currents. Thus, it is preferred that a metal which oxidizes more slowly than zirconium during passage of an electric current is employed in the region of the conductive layer most remote from the photoconductive layer of a metal, particularly where the ground plane is thin and must remain transparent to electromagnetic radiation and be electrically conductive throughout extended xerographic cycling. Metals and/or alloys which oxidize more slowly than zirconium during passage of an electric current include, for example, titanium, nickel, gold, stainless steel, silver, brass, platinum, vanadium, nichrome, molybdenum, and the like. Generally, for rear erase exposure, a conductive layer light transparency of at least about 15 percent is desirable. The conductive layer need not be limited to metals. Other examples of conductive layers may be combinations of materials such as conductive indium tin oxide as a transparent layer for light having a wavelength between about 400 nm (4000 Angstroms) and about 700 nm (7000 Angstroms) or a conductive carbon black dispersed in a plastic binder as an opaque conductive layer. Planar magnetrons are commercially available and are manufactured by companies such as the Industrial Vacuum Engineering Company, San Mateo, California, Leybold-Heraeus, Germany and U.S., and General Engineering, England. Magnetrons generally are operated at about 500 volts and 120 amps and cooled with water circulated at a rate sufficient to limit the water exit temperature to about 43°C or less. The use of magnetron sputtering for depositing a metal layer on a substrate is described, for example, in S-A-4,322,276. If desired, the zirconium layer may be formed by other suitable techniques such as in situ on the outer surface of the substrate which may be a metal layer or layer of any other suitable material. Regardless of the technique employed to form the zirconium layer, a thin layer of zirconium oxide forms on the outer surface of the zirconium upon exposure to air. Thus, when other layers overlying the zirconium layer are characterized as "contiguous" layers, it is intended that these overlying contiguous layers may, in fact, contact a thin zirconium oxide layer that has formed on the outer surface of the zirconuium layer. If the zirconium layer is sufficiently thick to be self supporting, no additional underlying member is needed and the zirconium layer may function as both a substrate and a conductive ground plane layer. Generally, a zirconium layer thickness of at least about 10 nm (100 angstroms) is desirable to maintain optimum resistance to charge deficient spots during xerographic cycling. A typical electrical conductivity for conductive layers for electrophotgraphic imaging members in slow speed copiers is about 10² to 10³ ohms/square. A thickness of at least about 2 nm (20 angstroms) of zirconium on a conductive substrate is sufficient to provide resistance to growth of charge deficient spots. The substrate may be opaque or substantially transparent and may comprise numerous suitable materials having the required mechanical properties. Accordingly, this substrate may comprise a layer of an electrically non-conductive or conductive material such as an inorganic or an organic composition. As electrically non-conducting materials there may be employed various resins known for this purpose including polyesters, polycarbonates, polyamides, polyurethanes, and the like. The electrically insulating or conductive substrate may be flexible or rigid and may have any number of many different configurations such as, for example, a plate, a cylindrical drum, a scroll, an endless flexible belt, and the like. Preferably, the substrate is in the form of an endless flexible belt and comprises a commercially available biaxially oriented polyester known as Mylar, available from E. I. du Pont de Nemours & Co. or Melinex available from ICI. The thickness of the substrate layer depends on numerous factors, including economical considerations, and thus this layer for a flexible belt may be of substantial thickness, for example, over 200 micrometers, or of minimum thickness less than 50 micrometers, provided there are no adverse affects on the final photoconductive device. If the photoreceptor is a rigid metal drum, the substrate layer can be 5000 micrometers thick. In one flexible belt embodiment, the thickness of this layer ranges from about 65 micrometers to about 150 micrometers, and preferably from about 75 micrometers to about 125 micrometers for optimum flexibility and minimum stretch when cycled around small diameter rollers, e.g. 12 millimeter diameter rollers. The surface of the substrate layer is preferably cleaned prior to coating to promote greater adhesion of the deposited coating. Cleaning may be effected by exposing the surface of the substrate layer to plasma discharge, ion bombardment and the like. The conductive layer may vary in thickness over substantially wide ranges depending on the optical transparency desired for the electrophotoconductive member. Accordingly, the zirconium metal layer thickness can generally range in thickness of from at least about 2 nm (20 angstrom units) to many centimeters. When a flexible photoresponsive imaging device is desired, the thickness may be between about 2 nm (20 angstrom units) to about 75 nm (750 angstrom units), and more preferably from about 5 nm (50 Angstrom units) to about 20 nm (200 angstrom units) for an optimum combination of electrical conductivity and light transmission. After deposition of the zirconium metal layer, a hole blocking layer is applied thereto. The zirconium layer without the hole blocking layer results in low charge acceptance and the formation of white or black spots (depending on whether positive or reversal imaging is employed) which is different in appearance from the spots encountered with the combination of a titanium ground plane and a blocking layer. Thus a blocking layer is necessary in combination with the zirconium layer to achieve low dark decay, adequate charge acceptance and any significant reduction in black or white spots caused by charge deficient spots. Generally, electron blocking layers for positively charged photoreceptors allow holes from the imaging surface of the photoreceptor to migrate toward the conductive layer. Thus, an electron blocking layer is normally not expected to block holes in positively charged photoreceptors such as photoreceptors coated with charge generating layer and a hole transport layer. Any suitable hole blocking layer capable of forming an electronic barrier to holes between the adjacent photoconductive layer and the underlying zirconium layer may be utilized.The hole blocking layer may be organic or inorganic and may be deposited by any suitable technique. For example, if the hole blocking layer is soluble in a solvent, it may be applied as a solution and the solvent can subsequently be removed by any conventional method such as by drying. Typical blocking layers include polyvinylbutyral, organosilanes, epoxy resins, polyesters, polyamides, polyurethanes, pyroxyline vinylidene chloride resin, silicone resins, fluorocarbon resins and the like containing an organo metallic salt. Other blocking layer materials include nitrogen containing siloxanes or nitrogen containing titanium compounds such as trimethoxysilyl propylene diamine, hydrolyzed trimethoxysilyl propyl ethylene diamine, N-beta-(aminoethyl) gamma-amino-propyl trimethoxy silane, isopropyl 4-aminobenzene sulfonyl, di(dodecylbenzene sulfonyl) titanate, isopropyl di(4-aminobenzoyl) isostearoyl titanate, isopropyl tri(N-ethylamino-ethylamino) titanate, isopropyl trianthranil titanate, isopropyl tri(N,N-dimethyl-ethylamino) titanate, titanium-4-amino benzene sulfonat oxyacetate, titanium 4-aminobenzoate isostearate oxyacetate, [H₂N(CH₂)₄]CH₃Si(OCH₃)₂, (gamma-aminobutyl) methyl diethoxysilane, and [H₂N(CH₂)₃]CH₃Si(OCH₃)₂ (gamma-aminopropyl) methyl diethoxysilane, as disclosed in US-A-4,291,110, US-A-4,338,387, US-A-4,286,033 and US-A-4,291,110. A preferred blocking layer comprises a reaction product between a hydrolyzed silane and the zirconium oxide layer which inherently forms on the surface of the zirconium layer when exposed to air after deposition. This combination reduces spots at time 0 and provides electrical stability at low RH . The hydrolyzed silane has the general formula: or mixtures thereof, wherein R₁ is an alkylidene group containing 1 to 20 carbon atoms, R₂, R₃ and R₇ are independently selected from the group consisting of H, a lower alkyl group containing 1 to 3 carbon atoms and a phenyl group, X is an anion of an acid or acidic salt, n is 1, 2, 3 or 4, and y is 1, 2, 3 or 4. The imaging member is prepared by depositing on the zirconium oxide layer of zirconium conductive anode layer a coating of an aqueous solution of the hydrolyzed silane at a pH between about 4 and about 10, drying the reaction product layer to form a siloxane film and applying electrically operative layers, such as a photogenerator layer and a hole transport layer, to the siloxane film. The hydrolyzed silane may be prepared by hydrolyzing a silane having the following structural formula: wherein R₁ is an alkylidene group containing 1 to 20 carbon atoms, R₂ and R₃ are independently selected from H, a lower alkyl group containing 1 to 3 carbon atoms, a phenyl group and a poly(ethylene)amino or ethylene diamine group, and R₄, R₅ and R₆ are independently selected from a lower alkyl group containing 1 to 4 carbon atoms. Typical hydrolyzable silanes include 3-aminopropyl triethoxy silane, (N,N′-dimethyl 3-amino) propyl triethoxysilane, N,N-dimethylamino phenyl triethoxy silane, N-phenyl aminopropyl trimethoxy silane, trimethoxy silylpropyldiethylene triamine and mixtures thereof. If R₁ is extended into a long chain, the compound becomes less stable. Silanes in which R₁ contains about 3 to about 6 carbon atoms are preferred because the molecule is more stable, is more flexible and is under less strain. Optimum results are achieved when R₁ contains 3 carbon atoms. Satisfactory results are achieved when R₂ and R₃ are alkyl groups. Optimum smooth and uniform films are formed with hydrolyzed silanes in which R₂ and R₃ are hydrogen. Satisfactory hydrolysis of the silane may be effected when R₄, R₅ and R₆ are alkyl groups containing 1 to 4 carbon atoms. When the alkyl groups exceed 4 carbon atoms, hydrolysis becomes impractically slow. However, hydrolysis of silanes with alkyl groups containing 2 carbon atoms are preferred for best results. During hydrolysis of the amino silanes described above, the alkoxy groups are replaced with hydroxyl groups. As hydrolysis continues, the hydrolyzed silane takes on the following intermediate general structure: After drying, the siloxane reaction product film formed from the hydrolyzed silane contains larger molecules in which n is equal to or greater than 6. The reaction product of the hydrolyzed silane may be linear, partially crosslinked, a dimer, a trimer, and the like. The hydrolyzed silane solution may be prepared by adding sufficient water to hydrolyze the alkoxy groups attached to the silicon atom to form a solution. Insufficient water will normally cause the hydrolyzed silane to form an undesirable gel. Generally, dilute solutions are preferred for achieving thin coatings. Satisfactory reaction product films may be achieved with solutions containing from about 0.1 percent by weight to about 1.5 percent by weight of the silane based on the total weight of the solution. A solution containing from about 0.05 percent by weight to about 0.2 percent by weight silane based on the total weight of solution are preferred for stable solutions which form uniform reaction product layers. It is important that the pH of the solution of hydrolyzed silane be carefully controlled to obtain optimum electrical stability. A solution pH between about 4 and about 10 is preferred. Thick reaction product layers are difficult to form at solution pH greater than about 10. Moreover, the reaction product film flexibility is also adversely affected when utilizing solutions having a pH greater than about 10. Further, hydrolyzed silane solutions having a pH greater than about 10 or less than about 4 tend to severely corrode metallic conductive anode layers such as those containing aluminum during storage of finished photoreceptor products. Optimum reaction product layers are achieved with hydrolyzed silane solutions having a pH between about 7 and about 8, because inhibition of cycling-up and cycling-down characteristics of the resulting treated photoreceptor are maximized. Some tolerable cycling-down has been observed with hydrolyzed amino silane solutions having a pH less than about 4. Control of the pH of the hydrolyzed silane solution may be effected with any suitable organic or inorganic acid or acidic salt. Typical organic and inorganic acids and acidic salts include acetic acid, citric acid, formic acid, hydrogen iodide, phosphoric acid, ammonium chloride, hydrofluorsilicic acid, Bromocresol Green, Bromophenol Blue, p-toluene sulfonic acid and the like. If desired, the aqueous solution of hydrolyzed silane may also contain additives such as polar solvents other than water to promote improved wetting of the metal oxide layer of metallic conductive anode layers. Improved wetting ensures greater uniformity of reaction between the hydrolyzed silane and the metal oxide layer. Any suitable polar solvent additive may be employed. Typical polar solvents include methanol, ethanol, isopropanol, tetrahydrofuran, methylcellosolve, ethylcellosolve, ethoxyethanol, ethylacetate, ethylformate and mixtures thereof. Optimum wetting is achieved with ethanol as the polar solvent additive. Generally, the amount of polar solvent added to the hydrolyzed silane solution is less than about 95 percent based on the total weight of the solution. Any suitable technique may be utilized to apply the hydrolyzed silane solution to the metal oxide layer of a metallic conductive anode layer. Typical application techniques include spraying, dip coating, roll coating, wire wound rod coating, and the like. Although it is preferred that the aqueous solution of hydrolyzed silane be prepared prior to application to the metal oxide layer, one may apply the silane directly to the metal oxide layer and hydrolyze the silane in situ by treating the deposited silane coating with water vapor to form a hydrolyzed silane solution on the surface of the metal oxide layer in the pH range described above. The water vapor may be in the form of steam or humid air. Generally, satisfactory results may be achieved when the reaction product of the hydrolyzed silane and metal oxide layer forms a layer having a thickness between about 2 nm (20 Angstroms) and about 200 nm (2,000 Angstroms). As the reaction product layer becomes thinner, cycling instability begins to increase. As the thickness of the reaction product layer increases, the reaction product layer becomes more non-conducting and residual charge tends to increase because of trapping of electrons and thicker reaction product films tend to become brittle. A brittle coating is, of course, not suitable for flexible photoreceptors, particularly in high speed, high volume copiers, duplicators and printers. The thicker coatings may, however, be acceptable in rigid photoreceptors. Drying or curing of the hydrolyzed silane upon the metal oxide layer should be conducted at a temperature greater than about room temperature to provide a reaction product layer having more uniform electrical properties, more complete conversion of the hydrolyzed silane to siloxanes and less unreacted silanol. Generally, a reaction temperature between about 100°C and about 150°C is preferred for maximum stabilization of electrochemical properties. The temperature selected depends to some extent on the specific metal oxide layer utilized and is limited by the temperature sensitivity of the substrate. Reaction product layers having optimum electrochemical stability are obtained when reactions are conducted at temperatures of about 135°C. The reaction temperature may be maintained by any suitable technique such as ovens, forced air ovens, radiant heat lamps, and the like. The reaction time depends upon the reaction temperatures used. Thus less reaction time is required when higher reaction temperatures are employed. Generally, increasing the reaction time increases the degree of cross-linking of the hydrolyzed silane. Satisfactory results have been achieved with reaction times between about 0.5 minute to about 45 minutes at elevated temperatures. For practical purposes, sufficient cross-linking is achieved by the time the reaction product layer is dry provided that the pH of the aqueous solution is maintained between about 4 and about 10. The reaction may be conducted under any suitable pressure including atmospheric pressure or in a vacuum. Less heat energy is required when the reaction is conducted at sub-atmospheric pressures. One may readily determine whether sufficient condensation and cross-linking has occurred to form a siloxane reaction product film having stable electric chemical properties in a machine environment by merely washing the siloxane reaction product film with water, toluene, tetrahydrofuran, methylene chloride or cyclohexanone and examining the washed siloxane reaction product film to compare infrared absorption of Si-O- wavelength bands between about 1,000 to about 1,200 cm⁻¹. If the Si-O- wavelength bands are visible, the degree of reaction is sufficient, i.e. sufficient condensation and cross-linking has occurred, if peaks in the bands do not diminish from one infrared absorption test to the next. It is believed that the partially polymerized reaction product contains siloxane and silanol moieties in the same molecule. The expression "partially polymerized" is used because total polymerization is normally not achievable even under the most severe drying or curing conditions. The hydrolyzed silane appears to react with metal hydroxide molecules in the pores of the metal oxide layer. This siloxane coating is described in US-A-4,464,450. The blocking layer should be continuous and have a thickness of less than about 0.5 micrometer because greater thicknesses may lead to undesirably high residual voltage. A blocking layer of between about 0.005 micrometer and about 0.3 micrometer (50 Angstroms - 3000 Angstroms) is preferred because charge neutralization after the exposure step is facilitated and optimum electrical performance is achieved. A thickness of between about 0.03 micrometer and about 0.06 micrometer is preferred for zirconium oxide layers for optimum electrical behavior and reduced charge deficient spot occurrence and growth. Optimum results are achieved with a siloxane blocking layer. The blocking layer may be applied by any suitable conventional technique such as spraying, dip coating, draw bar coating, gravure coating, silk screening, air knife coating, reverse roll coating, vacuum deposition, chemical treatment and the like. For convenience in obtaining thin layers, the blocking layers are preferably applied in the form of a dilute solution, with the solvent being removed after deposition of the coating by conventional techniques such as by vacuum, heating and the like. Generally, a weight ratio of blocking layer material and solvent of between about 0.05:100 and about 0.5:100 is satisfactory for spray coating. In some cases, intermediate layers between the blocking layer and the adjacent generator layer may be desired to improve adhesion or to act as an electrical barrier layer. If such layers are utilized, they preferably have a dry thickness between about 0.04 micron to about 5 microns. Typical adhesive layers include film-forming polymers such as polyester, polyvinylbutyral, polyvinylpyrolidone, polyurethane, polycarbonates polymethyl methacrylate, mixtures thereof, and the like. Any suitable photogenerating layer may be applied to the blocking layer or intermediate layer if one is employed, which can then be overcoated with a contiguous hole transport layer as described. Examples of photogenerating layers include inorganic photoconductive particles such as amorphous selenium, trigonal selenium, and selenium alloys selected from the group consisting of selenium-tellurium, selenium-tellurium-arsenic, selenium arsenide and mixtures thereof, and organic photoconductive particles including various phthalocyanine pigment such as the X-form of metal free phthalocyanine described in US-A-3,357,989, metal phthalocyanines such as vanadyl phthalocyanine and copper phthalocyanine, quinacridones available from DuPont under the tradename Monastral Red, Monastral violet and Monastral Red Y, Vat orange 1 and Vat orange 3 trade names for dibromo ant anthrone pigments, benzimidazole perylene, substituted 2,4-diamino-triazines disclosed in US-A-3,442,781, polynuclear aromatic quinones available from Allied Chemical Corporation under the tradename Indofast Double Scarlet, Indofast Violet Lake B, Indofast Brilliant Scarlet and Indofast Orange, and the like dispersed in a film forming polymeric binder. Selenium, selenium alloy, benzimidazole perylene, and the like and mixtures thereof may be formed as a continuous, homogeneous photogenerating layer. Benzimidazole perylene compositions are well known and described, for example in US-A-4,587,189. Multi-photogenerating layer compositions may be utilized where a photoconductive layer enhances or reduces the properties of the photogenerating layer. Examples of this type of configuration are described in US-A-4,415,639. Other suitable photogenerating materials known in the art may also be utilized, if desired. Charge generating binder layer comprising particles or layers comprising a photoconductive material such as vanadyl phthaocyanine, metal free phthalocyanine, benzimidazole perylene, amorphous selenium, trigonal selenium, selenium alloys such as selenium-tellurium, selenium-tellurium-arsenic, selenium arsenide, and the like and mixtures thereof are especially preferred because of their sensitivity to white light. Vanadyl phthalocyanine, metal free phthalocyanine and tellurium alloys are also preferred because these materials provide the additional benefit of being sensitive to infrared light. Numerous inactive resin materials may be employed in the photogenerating binder layer including those described, for example, in US-A-3,121,006. Typical organic resinous binders include thermoplastic and thermosetting resins such as polycarbonates, polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides, polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals, polyamides, polyimides, amino resins, phenylene oxide resins, terephthalic acid resins, epoxy resins, phenolic resins, polystyrene and acrylonitrile copolymers, polyvinylchloride, vinylchloride and vinyl acetate copolymers, acrylate copolymers, alkyd resins, cellulosic film formers, poly(amide-imide), styrene-butadiene copolymers, vinylidenechloride-vinylchloride copolymers, vinylacetate-vinylidenechloride copolymers, styrene-alkyd resins, and the like. These polymers may be block, random or alternating copolymers. The photogenerating composition or pigment is present in the resinous binder composition in various amounts, generally, however, from about 5 percent by volume to about 90 percent by volume of the photogenerating pigment is dispersed in about 10 percent by volume to about 95 percent by volume of the resinous binder, and preferably from about 20 percent by volume to about 30 percent by volume of the photogenerating pigment is dispersed in about 70 percent by volume to about 80 percent by volume of the resinous binder composition. In one embodiment about 8 percent by volume of the photogenerating pigment is dispersed in about 92 percent by volume of the resinous binder composition. The photogenerating layer containing photoconductive compositions and/or pigments and the resinous binder material generally ranges in thickness of from about 0.1 micrometer to about 5.0 micrometers, and preferably has a thickness of from about 0.3 micrometer to about 3 micrometers. The photogenerating layer thickness is related to binder content. Thinner layers with higher pigment loadings are preferred. Higher binder content compositions generally require thicker layers for photogeneration. Thicknesses outside these ranges can be selected providing the objectives of the present invention are achieved. The active charge transport layer may comprise any suitable transparent organic polymer or non-polymeric material capable of supporting the injection of photo-generated holes and electrons from the trigonal selenium binder layer and allowing the transport of these holes or electrons through the organic layer to selectively discharge the surface charge. The active charge transport layer not only serves to transport holes or electrons, but also protects the photoconductive layer from abrasion or chemical attack and therefor extends the operating life of the photoreceptor imaging member. The charge transport layer should exhibit negligible, if any, discharge when exposed to a wavelength of light useful in xerography, e.g. 400 nm (4000 angstroms) to 800 nm (8000 angstroms). Therefore, the charge transport layer is substantially transparent to radiation in a region in which the photoconductor is to be used. Thus, the active charge transport layer is a substantially non-photoconductive material which supports the injection of photogenerated holes from the generation layer. The active transport layer is normally transparent when exposure is effected through the active layer to ensure that most of the incident radiation is utilized by the underlying charge carrier generator layer for efficient photogeneration. When used with a transparent substrate, imagewise exposure may be accomplished through the substrate with all light passing through the substrate. In this case, the active transport material need not be transmitting in the wavelength region of use. The charge transport layer in conjunction with the generation layer in the instant invention is a material which is an insulator to the extent that an electrostatic charge placed on the transport layer is not conducted in the absence of illumination. The active charge transport layer may comprise an activating compound useful as an additive dispersed in electrically inactive polymeric materials making these materials electrically active. These compounds may be added to polymeric materials which are incapable of supporting the injection of photogenerated holes from the generation material and incapable of allowing the transport of these holes therethrough. This will convert the electrically inactive polymeric material to a material capable of supporting the injection of photogenerated holes from the generation material and capable of allowing the transport of these holes through the active layer in order to discharge the surface charge on the active layer. An especially preferred transport layer employed in one of the two electrically operative layers in the multilayer photoconductor of this invention comprises from about 25 to about 75 percent by weight of at least one charge transporting aromatic amine compound, and about 75 to about 25 percent by weight of a polymeric film forming resin in which the aromatic amine is soluble. The charge transport layer forming mixture preferably comprises an aromatic amine compound of one or more compounds having the general formula: wherein R₁ and R₂ are an aromatic group selected from the group consisting of a substituted or unsubstituted phenyl group, naphthyl group, and polyphenyl group and R₃ is selected from the group consisting of a substituted or unsubstituted aryl group, alkyl group having from 1 to 18 carbon atoms and cycloaliphatic compounds having from 3 to 18 carbon atoms. The substituents should be free form electron withdrawing groups such as NO₂ groups, CN groups, and the like. Typical aromatic amine compounds that are represented by this structural formula include: I. Triphenyl amines such as: II. Bis and poly triarylamines such as: Bis arylamine ethers such as: and IV. Bis alkyl-arylamines such as: A preferred aromatic amine compound has the general formula: wherein R₁, and R₂ are defined above and R₄ is selected from the group consisting of a substituted or unsubstituted biphenyl group, diphenyl ether group, alkyl group having from 1 to 18 carbon atoms, and cycloaliphatic group having from 3 to 12 carbon atoms. The substituents should be free form electron withdrawing groups such as NO₂ groups, CN groups, and the like. Examples of charge transporting aromatic amines represented by the structural formulae above for charge transport layers capable of supporting the injection of photogenerated holes of a charge generating layer and transporting the holes through the charge transport layer include triphenylmethane, bis(4-diethylamine-2-methylphenyl) phenylmethane; 4′-4″-bis(diethylamino)-2′,2″-dimethyltriphenyl-methane, N,N′-bis(alkylphenyl)-[1,1′-biphenyl]-4,4′diamine wherein the alkyl is, for example, methyl, ethyl, propyl, n-butyl, etc., N,N′-diphenyl-N,N′-bis(chlorophenyl)-[1,1′-biphenyl]-4,4′-diamine, N,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine, and the like dispersed in an inactive resin binder. Any suitable inactive resin binder soluble in methylene chloride or other suitable solvent may be employed in the process of this invention. Typical inactive resin binders soluble in methylene chloride include polycarbonate resin, polyvinylcarbazole, polyester, polyarylate, polyacrylate, polyether, polysulfone, and the like. Molecular weights can vary from about 20,000 to about 1,500,000. The preferred electrically inactive resin materials are polycarbonate resins have a molecular weight from about 20,000 to about 120,000, more preferably from about 50,000 to about 100,000. The materials most preferred as the electrically inactive resin material is poly(4,4′-dipropylidene-diphenylene carbonate) with a molecular weight of from about 35,000 to about 40,000, available as Lexan 145 from General Electric Company; poly(4,4′-isopropylidene-diphenylene carbonate) with a molecular weight of from about 40,000 to about 45,000, available as Lexan 141 from the General Electric Company; a polycarbonate resin having a molecular weight of from about 50,000 to about 100,000, available as Makrolon from Farbenfabricken Bayer A.G. and a polycarbonate resin having a molecular weight of from about 20,000 to about 50,000 available as Merlon from Mobay Chemical Company. Methylene chloride solvent is a desirable component of the charge transport layer coating mixture for adequate dissolving of all the components and for its low boiling point. Examples of photosensitive members having at least two electrically operative layers include the charge generator layer and diamine containing transport layer members disclosed in US-A-4,265,990, US-A-4,233,384, US-A-4,306,008, US-A-4,299,897 and US-A-4,439,507. As especially preferred multilayered photoconductor comprises a charge generation layer comprising a binder layer of photoconductive material and a contiguous hole transport layer of a polycarbonate resin material having a molecular weight of from about 20,000 to about 120,000 having dispersed therein from about 25 to about 75 percent by weight of one or more compounds having the general formula: wherein X is selected from the group consisting of an alkyl group, having from 1 to about 4 carbon atoms and chlorine, the photoconductive layer exhibiting the capability of photogeneration of holes and injection of the holes and the hole transport layer being substantially non-absorbing in the spectral region at which the photoconductive layer generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from the photoconductive layer and transporting the holes through the hole transport layer. Any suitable and conventional technique may be utilized to mix and thereafter apply the charge transport layer coating mixture to the charge generating layer. Typical application techniques include spraying, dip coating, roll coating, wire wound rod coating, and the like. Although it is preferred that the acid doped methylene chloride be prepared prior to application to the charge generating layer, one may instead add to acid to the aromatic amine, to the resin binder or to any combination of the transport layer components prior to coating. Drying of the deposited coating may be effected by any suitable conventional technique such as oven drying, infra red radiation drying, air drying and the like. Generally, the thickness of the hole transport layer is between about 5 to about 100 micrometers, but thicknesses outside this range can also be used. The hole transport layer should be an insulator to the extent that the electrostatic charge placed on the hole transport layer is not conducted in the absence of illumination at a rate sufficient to prevent formation and retention of an electrostatic latent image thereon. In general, the ratio of the thickness of the hole transport layer to the charge generator layer is preferably maintained from about 2:1 to 200:1 and in some instances as great as 400:1. If desired, any suitable single photoconductive layer capable of accepting a negative charge may be substituted for the combination of two electrically active layer described above. Typical single photoconductive layers include photoconductive particles such as zinc oxide, amorphous selenium, cadmium sulphide, vanadyl phthalocyanine, cadmium telluride, cadmium selenide, solid solutions thereof, and the like dispersed in an inactive film forming polymeric binder. Any suitable inactive film forming polymeric binder may be employed in the single photoconductive layer capable of accepting a negative charge. Typical organic film forming polymeric binders include thermoplastic and thermosetting resins such as polycarbonates, polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides, polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals, polyamides, polyimides, amino resins, phenylene oxide resins, terephthalic acid resins, epoxy resins, phenolic resins, polystyrene and acrylonitrile copolymers, polyvinylchloride, vinylchloride and vinyl acetate copolymers, acrylate copolymers, alkyd resins, cellulosic film formers, poly(amide-imide), styrene-butadiene copolymers, vinylidenechloride-vinylchloride copolymers, vinylacetate-vinylidenechloride copolymers, styrene-alkyd resins, and the like. These polymers may be block, random or alternating copolymers. The photoconductive composition or pigment is present in the resinous binder composition of the single photoconductive layer in various amounts, generally, however, from about 5 percent by volume to about 90 percent by volume of the photoconductive pigment is dispersed in about 95 percent by volume to about 10 percent by volume of the resinous binder, and preferably from about 10 percent by volume to about 30 percent by volume of the photoconductive pigment is dispersed in about 90 percent by volume to about 70 percent by volume of the resinous binder composition. In one embodiment about 25 percent by volume of the photoconductive pigment is dispersed in about 75 percent by volume of the resinous binder composition. The single photoconductive layer capable of accepting a negative charge generally ranges in thickness of from about 10 micrometer to about 40 micrometers, and preferably has a thickness of from about 20 micrometer to about 30 micrometers. Thickness outside these ranges can be selected providing the objectives of the present invention are achieved. Typical single photoconductive layers are described, for example, in US-A-3,121,006. Other layers such as conventional ground strips comprising, for example, conductive particles dispersed in a film forming binder may be applied to one edge of the photoreceptor in contact with the zirconium layer, blocking layer, adhesive layer or charge generating layer. Optionally, an overcoat layer may also be utilized to improve resistance to abrasion. In some cases a back coating may be applied to the side opposite the photoreceptor to provide flatness and/or abrasion resistance. These overcoating and backcoating layers may comprise organic polymers or inorganic polymers that are electrically insulating or slightly semi-conductive. Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings wherein: FIG. 1 is a schematic illustration of a prior art photoreceptor having a single metal ground plane. FIG. 2 is a schematic illustration of one embodiment of a photoreceptor of this invention having a plurality of ground planes. FIG. 3 is a schematic illustration of another embodiment of a photoreceptor of this invention having a plurality of ground planes. FIG. 4 graphically compares the light transmission characteristics of various ground planes during cycling. FIG. 5 is a plurality of photographs of xerographic copies made from originals of different densities on xerographic photoreceptors comprising various ground plane materials. In the drawings, FIGS. 1-3 represent several types of photoreceptor plates. They are basically similar and contain many layers that are common to the other photoreceptors. Referring to FIG. 1, a prior art photoreceptor is shown having an anticurl backing coating 1, a supporting substrate 2, a metal ground plane 3, a blocking layer 4, an adhesive layer 5, a charge generator layer 6, and a charge transport layer 7. In FIG. 2, a photoreceptor of this invention is illustrated. This photoreceptor differs from the photoreceptor shown in FIG. 1 in that an additional ground plane 8 is employed comprising zirconium. With referrence to FIG. 3, a photoreceptor of this invention is shown. This photoreceptor differs from the photoreceptor shown in FIG. 2 in that a thick rigid metal substrate 9 is employed rather than the anticurl backing coating 1, supporting substrate 2 and metal ground plane 3. In FIG. 4, the light transmission characteristics of various ground planes during cycling are compared under conditions described in Example IX. Referring to FIG. 5, print tests were performed at the start and end of cycling tests using normal xerographic development with photoreceptors having different ground planes. White spots in the solid image area of copies of originals having a density of 1.1 and 0.5 were counted and compared. Details of the procedures and results are described in Example IX. The electrophotographic member of the present invention may be employed in any suitable and conventional electrophotographic imaging process which utilizes negative charging prior to imagewise exposure to activating electromagnetic radiation. When the imaging surface of an electrophotographic member is uniformly charged with a negative charge and imagewise exposed to activating electromagnetic radiation, conventional positive or reversal development techniques may be employed to form a marking material image on the imaging surface of the electrophotographic imaging member of this invention. Thus, by applying a suitable electrical bias and selecting toner having the appropriate polarity of electrical charge, one may form a toner image in the negatively charged areas or discharged areas on the imaging surface of the electrophotographic member of the present invention. More specifically, for positive development, positively charged toner particles are attracted to the negatively charged electrostatic areas of the imaging surface and for reversal development, negatively charged toner particles are attracted to the discharged areas of the imaging surface. The electrophotographic member of the present invention exhibits fewer or no charge deficient spots prior to cycling, greater resistance to the formation of charge deficient spots during cycling, and improved resistance to the growth in size of charge deficient spots during cycling. The improvement relating to charge deficient spots provided by the electrophotographic imaging members of this invention is orders of magnitude greater that of photoreceptors utilizing a titanium ground plane. Photoreceptors with aluminum or titanium ground planes exhibit an increase in the number and size of charge deficient spots. Surprisingly, the electrophotographic member of present invention reduces during cycling the size and number of any charge deficient spots that might be present prior to cycling. Thus, any charge deficient spots intitially present in electrophotographic members having a zirconium ground plane appear to heal and disappear with cycling. The invention will now be described in detail with respect to the specific preferred embodiments thereof, it being understood that these examples are intended to be illustrative only and that the invention is not intended to be limited to the materials, conditions, process parameters and the like recited herein. All parts and percentages are by weight unless otherwise indicated. EXAMPLE I A polyester film was vacuum coated with a titanium layer having a thickness of about 20 nm (200 Angstroms). The exposed surface of the titanium layer was oxidized by exposure to oxygen in the ambient atmospnere. A siloxane hole blocking layer was prepared by applying a 0.22 percent (0.001 mole) solution of 3-aminopropyl triethoxylsilane to the oxidized surface of the aluminum layer with a gravure applicator. The deposited coating was dried at 135°C in a forced air oven to form a layer having a thickness of 12 nm (120 Angstroms). A coating of polyester resin, Goodyear PE100 (available from the Goodyear Tire an Rubber Co.) was applied with a gravure applicator to the siloxane coated base. The polyester resin coating was dried to form a film having a thickness of about 0.05 micrometer. A slurry coating solution of 3 percent by weight sodium doped trigonal selenium having a particle size of about 0.05 micrometer to 0.2 micrometer and about 6.8 percent by weight polyvinylcarbazole and 2.4 percent by weight N,N′-diphenyl-N,N′-bis(3 methyl phenyl)-[1,1′-biphenyl]-4,4′ diamine in a 1:1 by volume mixture of tetrahydrofuran and toluene was extrusion coated onto the polyester coating to form a layer having a wet thickness of 26 micrometers. The coated member was dried at 135°C in a forced air oven to form a layer having a thickness of 2.5 micrometers. A charge transport layer was formed on this charge generator layer by applying a mixture of a 60-40 by weight solution of Makrolon, a polycarbonate resin having a molecular weight from about 50,000 to about 100,000 available from Farbenfabriken Bayer A. G., and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine dissolved in methylene chloride to give a 15 percent by weight solution. The components were extrusion coated on top of the generator layer and dried at temperature of about 135 °C to form a 24 micrometer thick dry layer of hole transporting material. A grounaing strip coating and an anti curl backing coating were also applied. This photoreceptor was then cut and welded to form a continuous belt. The photoreceptor was then mounted in a Xerox 1065 machine for testing. The Xerox 1065 machine is a xerographic device which drives the photoreceptor belt at a constant speed of 28.6 cm (11.25 inches) per second. Charging devices, exposure lights, magnetic brush developer applicator and erase lights and probes are mounted around the periphery of the mounted photoreceptor belt. The photoreceptor was rested in the dark for 60 minutes prior to charging. It was then negatively corona charged in the dark to a development potential of -750 v. The photoreceptor was thereafter imagewise exposed to a test pattern using a light intensity of about 5 x 10⁻¹¹ J/m² (5 erg/cm²) of light. The resulting negatively charged electrostatic latent image was developed with positively chargea toner particles applied by a magnetic brush applicator. After electrostatic transfer of the deposited toner image to a paper copy sheet, the photoreceptor was discharged (erased) by exposure to about 500 x 10⁻¹¹ J/m² (500 erg/cm⁻² ) of light. The toner images transferred to the copy sheets were fused by heated roll fusing. The photoreceptor was then subjected to the equivalent life of 200,000 imaging cycles. After initial copies were made at ambient room conditions (about 35 percent RH and 70°F), the machine was then subjected to stress environmental conditions (10 percent RH, 70°F). The machine was cycled without feeding paper. At the end of the test, the machine was returned to ambient room conditions. Paper was fed into the machine for imaging. The toner image areas of the imaged copy sheets were examined with a 7x magnifying loupe for white spots. The area examined was a solid block rectangie( 3.6 cm x 6.4 cm) (1.4 inches x 2.5 inches) with a 1.1 density value. The number of white spots were circled and tabulated. The copy sheet from the first imaging cycle had 1 white spot and the copy sheet from the last imaging cycle had 75 white spots. These findings were used to determine growth rate per 100,000 imaging cycles by dividing (75 white spots - 1 white spot) by 2. Thus, the growth rate was + 37 white spots per 100,000 imaging cycles. EXAMPLE II The procedures of Example I were repeated with the same materials except that instead of being vacuum coated with a titanium layer, the polyester film was coated by sputtering in a vacuum in the absence of oxygen a zirconium metal layer having a thickness of about 20 nm (200 Angstroms). Utilizing the testing procedures of Example I, the photoreceptor was subjected to 200,000 imaging cycles. The toner image areas (3.6 cm x 6.4 cm) (1.4 inches x 2.5 inches and 1.1 density) of the imaged copy sheets were examined for white spots with a 7x magnifying loupe. The copy sheet from the first imaging cycle had 25 white spots and the copy sheet from the last imaging cycle had 8 white spots. This was a growth rate of -9 white spots per 100,000 imaging cycles with the zirconium metal layer of this invention. EXAMPLE III The procedures of Example I were repeated with the same materials except that instead of being vacuum coated only with a single titanium layer, the polyester film was coated by sputtering in a vacuum in the absence of oxygen a titanium metal layer having a thickness of about 6.5 nm (65 Angstroms). Without breaking the vacuum, the titanium layer was coated by sputtering, in the absence of oxygen, a zirconium metal layer having a thickness of about 12.5 nm (125 Angstroms). The exposed surface of the zirconium layer was oxidized by exposure to oxygen in the ambient atmosphere at elevated temperatures. Utilizing the testing procedures and conditions of Example I, the photoreceptor was subjected to 200,000 imaging cycles. The toner image areas of the imaged copy sheets were examined for white spots with a 7x magnifying loupe. The copy sheet from the first imaging cycle had 10 white spots and the copy sheet from the last imaging cycle had 35 white spots. This was a growth rate of + 13 white spots per 100,000 imaging cycles. EXAMPLE IV The procedures for preparing the photoreceptor belts in Example I were repeated except that the following materials were changed. The interface layer was a coating of polyester (duPont 49,000, available from E.I. duPont de Nemours & Co.) It was applied with a gravure applicator to the siloxane coated base. The polyester resin coating was dried to form a film having a thickness of about 0.05 micrometer. The same charge generator layer was applied as in Example I. The charge transport layers were the same materials as Example I. However, the ratios were 50-50 by weight solution of polycarbonate resin (Makrolon, available from Farbenfabrikan Bayer A. G.) and N,N′-diphenyl-N,N′-bis(3-methyl phenyl)-[1,1′-biphenyl]-4,4′-diamine dissolved in methylene chloride. All other materials and processes were the same as Example I. The photoreceptor was welded into a continuous belt and mounted on a Xerox 1075 duplicator used as a test fixture which drives the belt at a constant rate of 28.6 cm (11.3 inches) per second. The Xerox 1075 duplicator contained charging devices, exposure lights, magnetic brush developer applicator, and erase lights and probes mounted around the periphery of the mounted photoreceptor belt. The photoreceptor was rested in the dark for 15 minutes prior to charging. It was then negatively corona charged in the dark to a development potential of -800 volts. The resulting charge photoreceptors were developed with a reversal toner. Reversal toners form deposits in the discharged areas on the photoreceptor corresponding to the white areas on the copy paper. To accomplish reversal development, a bias voltage of 600 volts was applied to the developer applicator rolls. With reversal development, the charge deficient spots print out as black spots in the charged background areas on the copy paper. In this test sequence, the photoreceptor was continuously charged and developed with no light exposure. The test was accomplished at 20 percent RH. The resulting negatively charged electrostatic latent image was developed with negatively charged toner particles applied by the magnetic brush applicator. After electrostatic transfer of the deposited toner from charge deficient areas, the photoreceptor was recharged to maintain a development potential of 800 uniformly over the imaging surface. In this test, the photoreceptor was cycled continuously for 1 hour. A one square inch area was examined to measure the spot count. The titanium ground plane photoreceptors had an average of 68 spots per square inch. After one hour of cycling, the titanium ground plane photoreceptors had an average of 1450 spots per cm² (225 spots per square inch). This was a growth rate of + 157 white spots per hour of cycling. EXAMPLE V The procedures employed in Example IV were repeated except that instead of being vacuum coated with a titanium layer, the polyester film was coated by sputtering in a vacuum in the absence of oxygen a zirconium layer having a thickness of about 20 nm (200 Angstroms). Utilizing the test procedures described in Example IV, the photoreceptor was cycled for 1 hour. The copy sheet was examined for black spots in the same manner as described in Example IV. The copy sheet from the first cycle had 58 spots per square inch and the copy sheet after 1 hour of cycling had 574 spots per cm² (89 spots per square inch). This was a growth rate of only + 31 white spots per hour of cycling with the zirconium layer of this invention. EXAMPLE VI The procedures for preparing the photoreceptor belts in Example I were repeated except that the following materials were changed. The binder generator layer was a slurry coating solution of 0.5 percent by weight vanadyl phthalocyanine having a particle size of about 0.2 micrometer and about 4.5 percent by weight polycarbonate resin having a molecular weight of about 50,000 to about 100,000 (Makrolon, available from Farbenfabriken Bayer, A. G.) dissolved in methylene chloride to give a 5.0 precent by weight solids solution. The resulting photoreceptor was cut and welded to form a continuous belt. The photoreceptor was then mounted in a laboratory xerographic device which drove the photoreceptor belt at a constant speed of 17.3 cm(6.8 inches) per second. Charging devices, exposure lights, magnetic brush developer applicator, erase lights and probes were mounted around the periphery of the mounted photoreceptor belt. The photoreceptor was rested in the dark for 60 minutes prior to charging. It was then negatively corona charged in the dark to a development potential of -750 v. The photoreceptor was thereafter imagewise exposed to a test pattern using a light intensity of about 10⁻¹⁰ J/m² (10 erg/cm²) of light. The resulting negatively charged electrostatic latent image was developed with positively charged toner particles applied by a magnetic brush applicator. After electrostatic transfer of the deposited toner image to a paper copy sheet, the photoreceptor was discharged (erased) by exposure to about 500 x 10⁻¹¹ J/m² (500 erg/cm²) of light. The toner images transferred to the copy sheets were fused by heated roll fusing. The machine was then run for 20,000 copies. All of the copies were prepared at an ambient room condition of 35 percent RH and 70°F. The toner image areas of the imaged copy sheets were examined with a 7x magnifying loupe for total number of white spots. The area examined was a solid square block 1.27cm x 1.27cm (0.5 inch x 0.5 inch) with a 1.1 density value. The copy sheet from the first imaging cycle had 176 white spots and the copy sheet from the last imaging cycle had 212 white spots. The growth rate per 100,000 imaging cycles for this 1.6 cm² (0.25 square inch) solid area block was determined by multiplying (212 white spots - 176 white spots) by 5. Thus, the growth rate was + 160 white spots per 100,000 imaging cycles. EXAMPLE VII The procedures of Example VI were repeated with the same materials except that instead of being vacuum coated with a titanium layer, the polyester film was coated by sputtering in a vacuum in the absence of oxygen a zirconium metal layer having a thickness of about 20 nm (200 Angstroms). Utilizing the testing procedures of Example VI, the photoreceptor was subjected to 20,000 imaging cycles. The toner image areas (1.27 cm x 1.27 cm) (0.5 inch x 0.5 inch and 1.1 density) of the imaged copy sheets were examined for white spots with a 7x magnifying loupe. The copy sheet from the first imaging cycle had 10 white spots and the copy sheet from the last imaging cycle had 5 white spots. This was a growth rate of -25 white spots per 100,000 imaging cycles with the zirconium metal layer of this invention. EXAMPLE VIII The procedures employed in Example IV were repeated except that instead of being vacuum coated with a titanium layer, the polyester film was coated by sputtering in a vacuum in the absence of oxygen a zirconium layer having a thickness of about 20 nm (200 Angstroms). The silane blocking layer was omitted. All the remaining photoreceptor layers were coated as in Example IV. Utilizing the test procedures described in Example IV, the photoreceptor was cycled for 1 hour. The copy sheet was examined for black spots in the same manner as described in Example IV. The copy sheet from the first cycle had 23,407 spots per cm² (3,629 spots per square inch) and the copy sheet after 1 hour of cycling had 18,866 spots per cm² (2,925 spots per square inch). This test shows that a zirconium ground plane without the silane blocking layer is a poor, non-uniform blocking layer having many localized areas of charge injection. The spot count is two orders of magnitude higher without a blocking layer Example IX Sandwich structures having nominal 20 percent light transmission were prepared using pure Titanium, 30/70 volume ratio (38/62 weight ratio) Zirconium/Titanium, 50/50 volume ratio (59/41 weight ratio) Zirconium/Titanium, 70/30 volume ratio (77/23 weight ratio) Zirconium/Titanium, and pure Zirconium. The metals were applied to a transparent substrate with separate magnetron sputtering stations with the titanium deposited first and the zirconium deposited on top. Metal thicknesses were adjusted to obtain the 20% optical transmission with the Titanium to Zirconium ratios described above. Photoreceptors were made from these five combinations of substrates and ground planes by depositing coatings of a siloxane blocking layer, a polyester adhesive layer (PE-100, available from Goodyear Tire and Rubber Co.), a charge generating layer of trigonal selenium particles dispersed in a binder, and a polycarbonate resin and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine transport layer as described in Example I. Substrate oxidation rates were determined by placing circular dot shaped graphite paint conductive electrodes having a one square centimeter contact area on top of a portion of the photoreceptor. A constant current of one microamp was passed through these electrodes on the photoreceptor using a Trek 610a COR-A-TROL device. After a given number of cycles, one dot shaped electrode was removed. After another 9,000 cycles, another electrode was removed and so on for the cycle periods shown in the table below. The active organic layers of the photoreceptor under the dot shaped electrodes were removed by washing with methylene chloride and the transmission of the substrate under each dot shaped electrode was measured. A graph of transmission versus integrated current (charge) was then prepared to determine the change in substrate properties as a function of xerographic cycles. The conversion of charge to xerographic cycles was accomplished by dividing the total amount of charge passed through the sample by the amount of charge required for one xerographic cycle. For a photoreceptor with capacitance C per square centimeter charged to an initial potential V the charge per square centimeter Q is determined by Q = CV. In the test samples, the charge per square centimeter for one cycle was developed from a capacitance of 100 picofarads per square centimeter and an initial potential of 1,000 volts. The total amount of charge passed through the sample was divided by the amount of charge required for one xerographic cycle to determine an equivalent photoreceptor cycle. The results of the constant current cycling simulation are presented in the following Table and in Fig. 4. As shown in the Table above and in Fig. 4, pure zirconium layer initially exhibits about 24 percent light transmission capability and is entirely oxidized and more transparent after 280,000 cycles. The device with a pure titanium layer has changed in transmission characteristics from 20 percent to 26 percent over the same cycling interval. The multiple metal layer structures have an intermediate oxidation rate determined by the amount of titanium present. Photoreceptors were also made with fresh substrates identical to the substrates described above in this Example and tested for the equivalent of 200,000 cycles in a Xerox 1065 copier. Print tests were performed at the start and end of the test using normal xerographic development. White spots in a solid image area of a copy of an original having a density of 1.1 were counted and a density per square inch determined. The pure titanium and the multiple metal layer sandwich structures containing only a small amount of zirconium showed a significant increase in Charge Deficient Spots with a minimum increase in optical transmission while the pure zirconium sample showed a reduction in the level of Charge Deficient Spots with a rapid change in transmission. The samples with 50 percent and 70 percent Zirconium content showed a decrease in charge Deficient Spot level and reasonable transmission change with cycling. A comparison of white spots on copies of an original having a density of 0.5 are illustrated in the photographs located in the second, fourth and sixth rows of FIG. 5. Thus, for copies of originals having a range of densities such as photographic originals, many more white spots are encountered with photoreceptors having a titanium ground plane of 100 percent titanium. Although the invention has been described with reference to specific preferred embodiments, it is not intended to be limited thereto, rather those skilled in the art will recognize that variations and modifications may be amended which are within the scope of the claims.

Claims: An electrophotographic imaging member having an imaging surface adapted to accept a negative electrical charge, said electrophotographic imaging member comprising a substrate, a metal ground plane layer applied to the substrate, a hole blocking layer, a charge generation layer comprising photoconductive particles dispersed in a film forming resin binder, and a hole transport layer, said hole transport layer being substantially non-absorbing in the spectral region at which the charge generation layer generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from said charge generation layer and transporting said holes through said charge transport layer, characterized in that the metal ground plane layer comprises at least 50 per cent by weight zirconium. An electrophotographic imaging member according to Claim 1 wherein the combination of said metal ground plane layer and said blocking layer transmits at least 15 percent of light having a wavelength between about 400 nm and about 700 nm. An electrophotographic imaging member according to Claim 1 or Claim 2 wherein the metal ground plane comprises a zirconium layer overlying a titanium layer. An electrophotographic imaging member according to Claim 3 wherein said zirconium layer has a thickness of at least 2 nm. An electrophotographic imaging member according to any preceding claim wherein said metal ground plane layer comprising zirconium comprises a mixture of 50 percent by weight zirconium and 50 percent by weight of another metal. An electrophotographic imaging member according to any preceding claim including a layer of an adhesive material interposed between said blocking layer and said charge generation layer. An electrophotographic imaging member according to any preceding Claim wherein said blocking layer comprises a siloxane, said siloxane comprising a reaction product of a hydrolyzed silane having the structural formula wherein R₁ is an alkylidene group containing 1 to 20 carbon atoms and R₂ and R₃ are independently selected from the group consisting of H, a lower alkyl group containing 1 to 3 carbon atoms, a phenyl group, a poly(ethylene)amino group and an ethylene diamine group. An electrophotographic imaging member according to Claim 7 wherein said blocking layer comprising said siloxane has a thickness of between about 0.03 micrometer and about 0.06 micrometer. An electrophotographic imaging member according to any preceding Claim wherein said charge generating binder layer comprises particles or layers comprising a photoconductive material selected from the group consisting of vanadyl phthalocyanine, metal free phthalocyanine, benzimidazole perylene, trigonal selenium, selenium alloys selected from the group consisting of selenium-tellurium, selenium-tellurium-arsenic, selenium arsenide, and mixtures thereof. An electrophotographic imaging member according to any preceding claim wherein said charge generation layer has a thickness between about 0.1 micrometer and about 5 micrometers and wherein said generation layer comprises between about 5 percent and about 90 percent by volume of said photoconductive particles. An electrophotographic imaging member according to any preceding Claim wherein said hole transport layer comprises an organic polymer and an aromatic amine compound having the general formula: wherein R₁ and R₂ are an aromatic group selected from the group consisting of a substituted or unsubstituted phenyl group, naphthyl group, and polyphenyl group and R₃ is selected from the group consisting of a substituted or unsubstituted aryl group, alkyl group having from 1 to 18 carbon atoms and cycloaliphatic compounds having from 3 to 18 carbon atoms. An electrophotographic imaging member according to Claim 9 wherein said hole transport layer comprises a polycarbonate resin material having a molecular weight of from about 20,000 to about 120,000 and from about 25 to about 75 percent by weight of said diamine compound based on the total weight of said polycarbonate resin. An electrophotographic imaging member as claimed in any preceding claim, wherein the hole transport layer comprises a solid solution of a polycarbonate resin material and a diamine compound, said diamine compound having the general formula: wherein X is selected from the group consisting of an alkyl group having from 1 to about 4 carbon atoms and chlorine. An electrophotographic imaging member according to any preceding claim wherein said hole transport layer has a thickness between about 10 micrometers and about 40 micrometers.

Inventors: GONYEA FREDERICK D, GRABOWSKI EDWARD F, HORGAN ANTHONY M, PARIKH SATISH, ROBINSON CHARLES C, TOWERS HARVEY S, WIELOCH FRANCIS J, GONYEA, FREDERICK D., GRABOWSKI, EDWARD F., HORGAN, ANTHONY M., PARIKH, SATISH, ROBINSON, CHARLES C., TOWERS, HARVEY S., WIELOCH, FRANCIS J.
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 1988
Main classification: G03G5
IPC codes: G03G5