CN1196504A

CN1196504A - Photosensitive member, process for producing the same, and image forming apparatus and image forming method having the same

Info

Publication number: CN1196504A
Application number: CN98106915A
Authority: CN
Inventors: 青木诚; 植田重教; 桥爪淳一郎
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 1997-04-14
Filing date: 1998-04-14
Publication date: 1998-10-21
Anticipated expiration: 2018-04-14
Also published as: EP0872771A2; KR19980081387A; JPH10288852A; DE69801131D1; DE69801131T2; KR100289479B1; EP0872771B1; CN1126991C; EP0872771A3

Abstract

To improve the releasing property and slipperiness of a toner on the surface of a photosensitive member, the surface layer of the photosensitive member is formed of a non-single crystalline carbon film having a low spin density and a short spin relaxation time and containing at least hydrogen atoms, thereby providing a photosensitive member capable of forming a very precise and high-quality image and having a long life, and a photosensitive member having a high sensitivity, capable of not causing any defective image due to bleeding, and capable of stably obtaining a ghost-free, high-quality image without any change over time.

Description

Photosensitive part and preparation method thereof and imaging device and image formation method that these parts are arranged

The present invention relates to photosensitive part, its preparation method, the image processing system and the image forming method of photosensitive part are arranged.The present invention be more particularly directed in comprising the electrostatic image formation method of electrophotographic process with the photosensitive part of electronic photographic photosensitive component as typical case, it can obtain high precise image under various environment, even in the high speed processing process, use, because its high release characteristics, the fusing that also can not cause toner is bonding, and the sufficiently high operating characteristic of keeping this specific character is arranged, and high sensitivity is arranged, can stably obtain excellent picture; Also relate to its preparation method, have the image processing system of this photosensitive part and the image forming method that carries out with photosensitive part.

The component materials that the photosensitive part that forms as the electrostatic image that is used to comprise electrofax uses, suggestion is adopted such as selenium, cadmium sulfide, zinc paste, phthalocyanine and amorphous silicon (hereinafter referred to as " a-Si ").Wherein, propose so that to comprise silicon atom be on-monocrystalline deposited film principal ingredient, representational a-Si as the material of the photosensitive part that is used to have the high performance and long service life non-environmental-pollution, as an example, the on-monocrystalline deposited film of a-Si with hydrogen and 1 or halogen such as fluorine or chlorine compensate.The some of them of these materials are brought into use.U.S. Patent No. 4265991 has disclosed the technology of the electronic photographic photosensitive component that the relevant photoconductive layer that is mainly formed by a-Si constitutes.

The advantage of this a-Si type photosensitive part is that its surface has high rigidity, and the long wavelength light (770nm to 800nm) of noise spectra of semiconductor lasers etc. has high sensitivity, does not almost have because of using the degeneration that causes repeatedly.Therefore, be specifically designed to electro-photography apparatus, for example the photosensitive part of high speed copier and LBP (laser printer).

As the operation that forms this deposited film, many operations are being well-known in the art, as an example, have: sputter; Add hot CVD; The light assisted CVD; And plasma enhanced CVD.Specifically, plasma enhanced CVD, source gas is decomposed in the glow discharge of promptly wherein using DC current, high frequency (RF or VHF) or microwave to produce, form the operation of deposited film on the substrate of for example any expectation of glass, quartz, heat-resisting synthetic film, stainless steel or aluminium, it is by actual in forming the si deposition membrane process that electrofax is used widely.And disclosed various device.

In recent years, also make great efforts to attempt to improve film quality and processing characteristics, this was studied multiple measure.

Specifically,, for example have high discharge stability and can be used in and form for example insulating material of oxide film and nitride film, strengthen operation so be extensive use of the plasma that obtains by high frequency source because plasma strengthens the various advantages of operation.In recent years, as at " plasma chemistry and Cement Composite Treated by Plasma " vol.7, No. mention among (1987) pp.267-273, use the diode parallel-plate plasma to strengthen the CVD system, employing has the above high frequency electric source of 50MHz, and to carry out plasma enhanced CVD noticeable, under situation about not reducing by the deposited film performance that is higher than the conventional 13.56MHz discharge frequency acquisition of using, it demonstrates the ability of improving deposition rate.In relevant sputter, also reported to obtain higher discharge frequency by this way, and studied widely in recent years.

In recent years, owing to the requirement that has increased the high-quality replicated image, also very needing stably to provide the more technology of high picture quality.Duplicating machine is being increased under the situation of various requirement, for example require finer and closely woven, faster, digital processing, compact dimensions, reduce cost etc., so with there being more small particle diameter make toner, be that 0.005 to 0.008mm toner has become very popular by the particle diameter of the average weight of measurements such as Coulter counter.In order to obtain higher speed, there is this toner on its fixed performance, to improve, but does preventing bonding unfavorablely like this with the fusing of photosensitive part than small particle diameter, this is the performance of contradiction.Have itself also is bonding unfavorable to melting than small particle diameter.More particularly, when the toner removed by cleaning than small particle diameter, spill, must change the contact pressure of scraper plate in order to prevent toner.But,, cause melting bonding tendency so we can say that toner has because friction force is along with high speed processing increases simultaneously.

If toner and photosensitive drum surface fusing are bonding, because the position of image exposure is not melted bonding region by toner, so do not form latent image, thin stain appears in this zone on image.And in case it is bonding fusing to occur, although do not appear on the copied image at initial period, along with the repetition of replicate run, the fusing of growing on sense of rotation is bonding, and the result produces the linearity defect picture.Can only be bonding by scrape the fusing that the photosensitive part surface removal produces like this with aluminium powder etc., just can remove the bonding toner of fusing.But actual mode is to change a new photosensitive part, thereby causes the increase of operating cost.Therefore, need prevent bonding appearance and the increase of toner fusing.

As the technology that overcomes these problems, in the prior art, following method is well-known.At first, as the method that make to be difficult for the scratch surface, comprise that many documents of Japanese Patent Application Publication No.57-114146 for example disclose, well-known is to form superficial layer with amorphous carbon (atomic carbon) that is called a-c or DLC (diamond-like-carbon).As the method that changes superficial layer, as disclosing in U.S. Patent No. 4661427 and Japanese Patent Application Publication No.61-160754, the spin density that changes the surface is well-known.

But, in the described in front faster and finer and closely woven trend, do not give one's full attention to the relaxation property and the smooth property of toner on superficial layer.More particularly, bonding in order not produce the toner fusing, a kind of consideration countermeasure is to change the surface, makes toner be difficult for adhering to photosensitive part, or makes scraper plate possess higher hardness, so that strengthen the ability that scrapes bonding toner.But because along with processing speed increases, friction force increases and abrasive power increases, thus there is such possibility, even should become more effective in the surface, unless but select material meticulously, otherwise will abrade the surface of photosensitive part undesirably.Have, its performance has broken away from rubbery state, and is tending towards glassy state again, and therefore, scraper plate becomes fragile with quality of materials, so exist the scraper plate fragmentation to cause the possibility of cleaning fault.Therefore, at present considered to be provided with the photosensitive part of surface or superficial layer, they have higher hardness, even under the condition of inclement condition on the drum surface, for example use to have under the situation of small particle diameter toner, also do not scrape the surface of photosensitive part, and change over that not produce the toner fusing bonding in high speed processing, even and after duplicating a large amount of paper for a long time, can not make its functional deterioration yet.

Duplicating machine is being increased under the situation of various requirement, and electronic photographic photosensitive component also needs to possess higher sensitivity, to obtain high quality image and to have thin film thickness.In this case, the superficial layer on protection photosensitive part surface need reduce damage and form film.Therefore, at present attempted providing have wide band (band) crack, high-breakdown-voltage intensity and can make the surface layer material of film more.

The object of the present invention is to provide the photosensitive part that can address the above problem, it has improved release performance and smooth property on superficial layer (surface region), make the fusing that under every kind of environment, can not occur in the toner on the photosensitive part bonding, can obtain high meticulous and high-quality image and very long thickness is arranged.

Another object of the present invention provides a kind of photosensitive part, and it has high sensitivity, can not produce any defective image that causes because of leakage, can stably obtain not have ghost image and high-quality image, and any change can not arranged in time.

For achieving the above object, the invention provides a kind of photosensitive part, comprise the substrate that has conductive surface, be arranged at this district, photoconduction district on the substrate and preferably include the non-single-crystal material that mainly constitutes and forms and be arranged at the surface region that forms in the photoconduction district by silicon atom;

With low spin density and the spin relaxation time of lacking being arranged and comprising that at least the on-monocrystalline carbon film of hydrogen atom forms surface region.

The present invention also provides a kind of image processing system, comprising:

Photosensitive part comprises electrically-conductive backing plate, is arranged at the photoconduction district on the substrate and is arranged at the surface region that photoconduction is distinguished, and uses the spin relaxation time that low spin density and weak point are arranged and comprises that at least the on-monocrystalline carbon film of hydrogen atom forms surface region;

Charger charges to the photosensitive part surface electrostatic;

Light source is to the photosensitive part face exposure;

Developer, the electric charge according to keeping from the teeth outwards provides toner to the photosensitive part surface;

Transfer device, the toner on photosensitive part surface is supplied with in transfer printing;

Clearer cleans photosensitive parts surface.

The present invention also provides a kind of image forming method, comprises the following steps:

To the charging of photosensitive part surface electrostatic, this photosensitive part comprises electrically-conductive backing plate, is arranged at the photoconduction district on the substrate and is arranged at the surface region that photoconduction is distinguished; With low spin density and the spin relaxation time of lacking being arranged and comprising that at least the on-monocrystalline carbon film of hydrogen atom forms surface region;

Photosensitive part exposure to charging;

Form the toner image on the photosensitive part surface according to exposure;

Transfer printing toner image; With

After transfer printing toner image, clean photosensitive parts surface.

The present invention also provides a kind of method for preparing photosensitive part, comprises the following steps:

The atmosphere that is formed in the chamber that can be evacuated and have substrate is applied energy, and this atmosphere comprises carbon atom and the hydrogen atom under the decompression state, and forms the photoconduction district on this substrate; With

Produce plasma thus, form surface region in the photoconduction district, this surface region is by the spin relaxation time with low spin density and weak point and comprise that at least the on-monocrystalline carbon film of hydrogen atom constitutes.

Like this, in the present invention, considered spin density and spin relaxation time in the surface region,, can prevent that toner is bonding to the fusing on photosensitive part surface so that can on release property and smooth property, improve toner.

Owing to can prevent that toner is bonding to the fusing on photosensitive part surface,, can form high fine and closely woven and high-quality image and long-life photosensitive part is arranged so that can be provided with so be easy to use toner than small particle diameter.

Figure 1A is the schematic sectional view of expression according to single-layer type photosensitive part of the present invention; Figure 1B is the schematic sectional view of expression according to function divergence type photosensitive part of the present invention.

Fig. 2 is expression is used for forming with PCVD the deposition system example of photosensitive layer on substrate a synoptic diagram.

Fig. 3 is expression is used for forming with VHF-PCVD the deposition system example of photosensitive layer on substrate a synoptic diagram.

Fig. 4 is that expression is with the schematic sectional view of image processing system of the present invention as electro-photography apparatus.

Photosensitive part of the present invention has electrically-conductive backing plate, at photoconduction district that is provided with on the substrate and the surface region that in the photoconduction district, is provided with.By having low spin density, forming surface region than the short on-monocrystalline carbon film that also comprises hydrogen atom slack time at least that spins.

In photosensitive part of the present invention, photoconduction district and surface region can be respectively photoconductive layer and superficial layer.

In photosensitive part of the present invention, the on-monocrystalline carbon film preferably has 1 * 10 ²⁰Spin (spin)/cm ³Or lower spin density and 10 ^-2Second or littler spin slack time.

In photosensitive part of the present invention, the on-monocrystalline carbon film preferably also comprises fluorine atom in film.

In photosensitive part of the present invention, the on-monocrystalline carbon film in its surface or near surface preferably also have the fluoro-carbon bond.

The most handy source gas that comprises fluorine atom forms the on-monocrystalline carbon film of photosensitive part of the present invention.

It is better to corrode the on-monocrystalline carbon film that forms photosensitive part of the present invention by the plasma that produces with the source gas that comprises fluorine atom.

Preferably CF ₄Gas is as the source gas generation photosensitive part of the present invention that comprises fluorine atom.

In photosensitive part of the present invention, preferably adopt plasma enhanced CVD (chemical vapor deposition) decomposition gas of 1 to 450MHz high frequency to form superficial layer.

In photosensitive part of the present invention, preferably adopt plasma enhanced CVD (chemical vapour deposition) decomposition gas of 50 to 450MHz high frequencies to form superficial layer.

Between photoconduction district (floor) and surface region (floor), the intermediate medium district of component intermediate that between is arranged preferably is provided with photosensitive part of the present invention as buffer zone.

The present invention of above-mentioned formation finishes as the following result of study that the inventor did.

The inventor prepares several on-monocrystalline carbon films more much longer than the life-span of conventional surface layer material that are considered to, to it (wherein as extensive studies, the on-monocrystalline carbon film mainly refers to can exist with polycrystalline or crystallite for neither graphite neither adamas but amorphous carbon-film under the intermediate state of the key between them).

, only, the frequency that melts bonding generation is not brought influence by making to have the superficial layer of high rigidity.Increase the hardness or the contact pressure of scraper plate, when fusing is bonding, can wipe toner immediately, wish that in this direction improvement is arranged.But on the contrary, the discovery scraper plate becomes and causes the grievous injury of mistake cleaning continually.That is, clear, only by making superficial layer have high rigidity to prevent to melt the bonding limitation that has.

Then, they have carried out extensive studies to the release performance aspect of improving the surface.As a result, they chance on, at the spin density on surface and the correct relation between the toner release performance.

Below, utilizing the on-monocrystalline carbon film that high like this hardness is arranged so that be difficult to wipe off, they study the film that little spin density is arranged.As a result, find release performance and smooth property than this performance improvement of conventional surface layer material a lot.,, find after long-time the duplicating, in most cases can not to keep these performances, be difficult to obtain to keep the film of these performances even when superficial layer has above-mentioned performance simultaneously.

After this, in further research process, the inventor finds, there is the small number of combinations of on-monocrystalline carbon of low spin density not talkative effectively, only this on-monocrystalline carbon film, promptly have than some specific range of values more among a small circle spin density and the on-monocrystalline carbon film of the spin relaxation time shorter than some value at release performance and smooth property direction improvement is arranged, even after long-time the duplicating, such superficial layer performance does not reduce yet, and is difficult to cause that fusing is bonding.

More particularly, there is the on-monocrystalline carbon film of the hardness that is higher than conventional material to make surface layer material when using, and forms this film like this, make its spin density be lower than 1 * 10 ²⁰Spin/cm ³, the spin relaxation time is lower than 10 ^-2During second, just might improve release performance and smooth property, can also keep these performances and be difficult to that fusing takes place for the first time bonding.

Why can prevent to melt bonding and can keep the reason of the performance expected when forming the on-monocrystalline carbon film within the scope of the present invention and unclear, but can be estimated as follows: compare with conventional surface layer material, the on-monocrystalline carbon film of Xing Chenging can improve the duplicating performance in the starting stage under given conditions.When forming the on-monocrystalline carbon film under suitable condition, promptly use hydrogen atom termination on-monocrystalline carbon film surface, think that film has so low surface free, it is thereon bonding that substrate is difficult to, and promptly can improve release performance.With atomic force microscope observation as can be known, with optimum filming condition or suitably handle, be formed on film smooth on the atomic energy level.Estimate that this is a reason of improving smooth property.

, when having a large amount of dangling bonds from the teeth outwards, they absorb the increase that various materials (matter) cause surface free energy thereon as absorbent core, cause the infringement of release performance.Simultaneously, think that each composition viscosity also makes smooth property poor.Following estimation, if under the condition that repeats to rub with the drum periphery on the surface, surface atom comes off, thereby total energy produces dangling bonds.Under such vicious cycle, the toner fusing is bonded in privileged sites, in case there has been fusing bonding on it, melts bonding just growth around it, occurs on image.

In the on-monocrystalline carbon film, compare with conventional a-Si or SiC and to be difficult to control its spin density., under specific condition, can obtain low spin density and promptly be lower than 1 * 10 ²⁰Spin/cm ³The film that is used for the on-monocrystalline carbon film.This can improve release performance more in the starting stage, but finds that the vicious cycle that produces dangling bonds still takes place after long-time the use.According to this fact, think and need reduce the dangling bonds quantity of existence from the teeth outwards or the bonding of reinforcement such as the dvielement of the hydrogen that is terminated at the surface in the starting stage, restrain dangling bonds and produce.Reducing dangling bonds in the starting stage has limitation, and has restriction to strengthening with the bonding of termination element.

When bonding force with the termination element is strengthened in expectation, think with the bonding of the carbon surrounding of termination element bonding in less stress is arranged.If bonded carbon under stress with bonding on every side, think that linkage electron becomes inhomogeneous, close with termination element weak bond.Think that the linkage electron that is caused by bonding stress glimmers, be viewed as waveshape with ESR (absorption of electronics rotary harmonic), think that the spin relaxation time just becomes shorter with bonding is more stable, think that bonding has littler stress with the spin relaxation time is shorter, promptly sets up firm bonding.So think, if form superficial layer, be the surface of the spin relaxation time of weak point, the termination element just can not come off, and the vicious cycle of dangling bonds never takes place to produce.

In sum, if, be lower than 1 * 10 owing to use the on-monocrystalline carbon film and control its spin density even also do not cause the photosensitive part that fusing is bonding after having obtained under high-speed process, to work long hours ²⁰Spin/cm ³, thereby in the starting stage, it can improve release performance and smooth property greatly, and because its spin relaxation time of control is lower than 10 ^-2Second, therefore can keep this performance.

When with fluorine atom termination on-monocrystalline carbon film surface, this film can have extremely low surface free energy, and can improve release performance and smooth property better.The reinforcement of this bonding force, the coming off of bigger ground limiting surface atom, thereby it is bonding enough situations such as element terminations such as hydrogen atoms more to be difficult to produce fusing.

The available following method termination (hereinafter referred to as " fluoridizing ") of fluorine atom: with fluoro-gas such as CF ₄Deng importing, fluorine atom is mixed in the film that film forming begins, or after forming the on-monocrystalline carbon film, fluoridize this surface with the plasma of fluoro-gas.In previous method, if fluorine accounts for too vast scale in film forming gas, just may cause mantle, as long as but gas ratio is set, can provide within the scope of the present invention spin density and spin relaxation time, just can keep hardness so.Its reason is unclear, thereby supposes can keep hardness because of bonded energy grow within the scope of the present invention.In a kind of method in back, importantly consider to handle not injured surface with fluoro plasma.If surface damage, surface atom is amassed wealth by heavy taxation possibly, thereby necessary fluorinated surface, so that spin density and the spin relaxation time in the scope of the invention to be provided.

In addition, surprising advantages of the present invention is, can make the caused any reduction of superficial layer keep minimum, can prevent preferably that ghost phenomena from being that the phenomenon of residual previous printing image and the feasible layer thickness that can be very little of improvement of voltage breakdown form superficial layer sensitivity.

Above-mentioned three surprising advantages are carried out following supposition:

Measure the band gap of the on-monocrystalline carbon film of the present invention's announcement, this film has than the bigger band gap of conventional a-C film.Infer this be because: because of reducing dangling bonds and increase firm key, thereby the bonding force of whole film increases, and optical band gap is wideer.Even have under the situation of bigger improvement at identical layer thickness, to sensitivity, this wide band gap also can make loss be lower than situation among the conventional a-C.

As for ghost image, think that catching electric charge because of energy level takes place.In the present invention, infer that the energy level of catching electric charge is reduced, get across that this thin surface layer thickness is several thousand dusts at the most, think to relate to some different factors but can not only be used in the energy level that exists in the thin list surface layer.But details is unclear.

Usually, in the on-monocrystalline carbon film, the activation part when forming will easily cover the photosensitive part surface, thereby can improve coverage, and within the scope of the present invention, except that good coverage, also can improve density greatly.Infer that high-compactness para-linkage state has contribution, but present not clear its details.Infer, because good coverage, all can be vinegar-pepper equably by any defective that peripheral projecting part etc. causes, and, because of the high-compactness electric charge is difficult to by around the defective part, thereby improve voltage breakdown, make it be difficult to cause the clear area, the clear area may be caused by the charge discharging resisting from superficial layer.

The present invention finishes by above-mentioned research.

Describe the present invention with reference to the accompanying drawings in detail.

Figure 1A and 1B are the schematic cross sectional view of expression electronic photographic photosensitive component layer structure of the present invention.Figure 1A illustrates the photosensitive part that is called single-layer type, and its photosensitive layer does not separate from function, and this photosensitive part comprises: substrate 101; The electric charge of configuration injects restraining barrier (electric charge injection Resistance) 102 selectively on substrate 101; Be stacked and placed on the photoconductive layer (photoconduction district) 103 that forms and comprise at least hydrogen atom on this restraining barrier by a-Si; With the superficial layer (surface region) 104 that forms, has feature of the present invention by on-monocrystalline carbon.

Figure 1B represents to be called the photosensitive part of function divergence type, and its photoconductive layer is separated into charge generation layer and electric charge transmission (transport) layer from function.On the surface of substrate 101, dispose electric charge selectively and inject restraining barrier 102, and stacked form and comprise at least the photoconductive layer 103 of hydrogen atom thereon by a-Si, this photoconductive layer 103 is separated into charge generation layer 106 and electric charge transport layer 105 from function.On this layer, be stacked and placed on the superficial layer 104 that forms, has feature of the present invention by on-monocrystalline carbon.Wherein, can under the relation of any position, use charge generation layer 106 and electric charge transport layer 105.In addition, when the change component carries out the function separation, can carry out component in a continuous manner and change.

In the photosensitive part shown in Figure 1A and the 1B, each layer can have continuous component to change, and maybe can not have tangible interface.Can omit electric charge when needing and inject restraining barrier 102.For for example improving the purpose of viscosity, transition bed (zone of transition) 104 also can be disposed at photoconductive layer 103 selectively and the superficial layer 104 that forms by on-monocrystalline carbon between.Transition bed can be formed by the material that comprises SiC, has the layer of the component transition between photoconductive layer 103 and superficial layer 104 with formation, or also can form this layer by SiO, SiN etc.Transition bed also has continuously changing of component.

Here, on-monocrystalline carbon master more refers to have the amorphous carbon of the natural intermediate between graphite and adamas, and can comprise crystallite or polycrystalline in the part.Can form these films with plasma enhanced CVD, sputter, ion injection etc.The film that forms with plasma enhanced CVD has high transparent and high rigidity, is suitable for use as the superficial layer of electronic photographic photosensitive component.

When forming the on-monocrystalline carbon film, available any frequency is as the discharge frequency of using in plasma enhanced CVD.The high frequency that is called RF of industrial preferred 1～450MHz, especially 13.56MHz.Particularly, when use 50～450MHz be called the high frequency of VHF the time, can improve the transparency and hardness better, thereby it is better to be used to form superficial layer.

Forming under the situation of on-monocrystalline carbon film of the present invention with plasma enhanced CVD, using the plasma decomposes carbonaceous gas, thereby forming film.The carbonaceous gas that is applicable to this situation can comprise such as CH ₄, C ₂H ₆, C ₂H ₄And C ₂H ₂And so on hydrocarbon gas; With bubble (bubbling) as CH ₃OH and C ₂H ₅OH and so on has the gas of the alcohol preparation of hydrogen; With replace as CH with halogen atom ₃F, CH ₂F ₂And CH ₃The halogenated hydrocarbon gas of the hydrogen atom preparation of hydrocarbon such as CI; As long as when forming plasma, can produce active carbon back, then anyly also all can use.In these some may be separately formed film, and some must dilute with hydrogen or diluents.Must select top condition to each situation.Any mixed gas in the above-mentioned gas also all can use.

The schematically illustrated the present invention of Fig. 2 prepares the example of photosensitive part by the plasma enhanced CVD that uses high frequency electric source.

Say that roughly this system comprises: deposition system 2100, source gas delivery system 2200 and to the exhaust system (not shown) of reactor 2110 exhaust gas inside.In the reactor 2110 in deposition system 2100, dispose the cylindric substrate for film deposition 2112 of ground connection, be used to heat the well heater 2113 and the source gas transmission pipeline 2114 of cylindric substrate for film deposition 2110.High frequency electric source 2120 links to each other with this reactor by high frequency matching box 2115.

Source gas delivery system 2200 is useful on as SiH ₄, H ₂, CH ₄, C ₂H ₂, NO, B ₂H ₆And CF ₄Deng source gas and the inflator 2221～2226 of etchant gas, valve 2231～2236,2241～2246 and 2251～2256, flow controller 2211～2216.The gas cylinder that is used for each composition gas links to each other with gas transmission pipeline 2114 at reactor 2110 by valve 2260.

As long as can produce be applicable in 10W～5000W scope or more than the output power of the equipment used, the high frequency electric source that so just can use the power supply of any output to use do the present invention.Considering high frequency electric source output pulsation degree, can be any value that obtains effect of the present invention.

Only can make high frequency electric source 2120 and load matched, the matching box that can use any structure is as high frequency matching box 2115.As the method for coupling, can automatically control, or artificially control, and to the present invention without any negative interaction.

The combination of available copper, aluminium, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, tantalum, stainless steel and two or more these materials is as negative electrode (reactor madial wall) material that applies high frequency electric source.Negative electrode preferably has cylindrical shape, can select ellipse or polygon.Because of the distance between substrate 2112 and the negative electrode can remain unchanged, so preferably make negative electrode that the configuration that is similar to substrate 2112 shape of cross sections is arranged.

Negative electrode can dispose cooling device arbitrarily.As concrete cooling device, can select water, air, liquid nitrogen, peltier device to wait cooling electrode as required.

Cylindric substrate for film deposition 2112 can be made of any material, according to its application Any shape can be arranged.For example, when producing electronic photographic photosensitive component, its shape is preferably cylindric, maybe can select plate shaped or any other shape.As baseplate material, the combination of available copper, aluminium, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, tantalum, stainless steel and two or more these materials, and as the paper of polyester, tygon, polycarbonate, acetate fiber, polypropylene, Polyvinylchloride, polyvinylidene chloride, polystyrene, glass, quartz, pottery and coated with conductive material.Certainly, select these according to membrance casting condition, application etc.Be the purpose that for example prevents to disturb, available cutting or indentation method form its surface.

The following describes the preferred embodiment that forms the job operation of the photosensitive part of system shown in Fig. 2.

Cylindric substrate for film deposition 2112 is arranged in the reaction chamber 2110, with exhaust apparatus (not shown, for example vacuum pump) reaction chamber 2110 inside is vacuumized.Then, utilize the well heater 2113 of the cylindric substrate for film deposition of heating, control the predetermined temperature in the temperature to 20 ℃ of the cylindric substrate for film deposition 2112～500 ℃ scope.

Before the source gas that is used to form photosensitive part flows into reaction chamber 2110, check the air-outlet valve 2117 of gas cylinder valve 2231～2236 and reaction chamber, determine that they are closed, and check flow valve 2241～2246, flow out valve 2251～2256 and auxiliary valve 2260, determine that they open.Then, open main valve 2118, the inside of reaction chamber 2110 and gas transmission pipeline 2116 is vacuumized.

Then, be designated as 5 * 10 when reading of vacuum meter 2119 ^-6During torr pressure, close auxiliary valve 2260 and flow out valve 2251.Therefore, open gas collecting jar with ground-on cover plate valve 2231～2236, gas is imported from gas collecting jar with ground-on cover plate 2221～2226 respectively, and to control each gaseous tension with work pressure controller 2261～2266 be 2kg/cm ²Then, slowly open flow valve 2241～2246, make gas flow into flow controller 2211～2216 respectively.

After beginning, at first on cylindric substrate for film deposition 2112, form photoconductive layer by said process preparation film forming.

More particularly, reach in the predetermined temperature in cylindric substrate for film deposition 2112, some necessary valves and auxiliary valve 2260 in flowing out valve 2251～2256 are slowly opened, so that from gas cylinder 2221～2226 gas is sent into reaction chamber 2110 by gas transmission pipeline 2114.Then, operations flows amount controller 2211～2216 is regulated each source gas and is flowed with set rate.Under the sort of situation, the branch (divergence) that regulates main valve 2118 observes vacuum gauge 2119 simultaneously, makes the pressure in the reaction chamber 2110 reach the predetermined pressure that is not higher than 1 torr.When the internal pressure change is stablized, by predetermined power source high frequency electric source 2120 is set, by high frequency matching box 2115 it is supplied with negative electrode, so produce the high frequency glow discharge.The source gas of sending into reaction chamber 2110 decomposes because of the discharge energy that produces like this, so that mainly the predetermined illuvium that is made of silicon forms on cylindric substrate for film deposition 2112.After the film that forms predetermined thickness, stop the supply high frequency power supply, to close and flow out valve 2251～2256, the source gas of making stops to flow into reaction chamber 2110.So just, finished the formation of photoconductive layer.

When on photoconductive layer, forming superficial layer, can repeat aforesaid operations basically, film forming gas is imported to begin discharge.Forming effect of the present invention before the contributive on-monocrystalline carbon film, must gases used kind with mixing ratio, become film pressure, high frequency electric source and its frequency, film-forming temperature etc. to be arranged on suitable value., this and do not mean that and need any special equipment.Can form this film with any conventional plasma enhanced CVD system.

Difference according to gaseous species can have different gas mixture ratios, can not illustrate utterly.For example, close the hydrocarbon gas diluted in hydrogen, close hydrocarbon gas then without diluted in hydrogen for full for insatiable hunger.As for becoming film pressure, can with the pressure of conventional membrance casting condition uniform pressure scope under film forming.It is decided according to gaseous species, can not say utterly.Such trend is arranged, and pressure is provided with better lowly, presses the polymerization that vapour phase takes place with restriction.As for high frequency electric source, unless the discharge energy that is higher than certain level is provided, c h bond closes and can not be cut off and can not form base.If too high discharge energy is provided on the other hand, may take place so to discharge again and sputter, undesirably make rate of film build extremely low.When with coaxial circles tubular film forming stove, the power that is lower than about 2000W is better.With regard to frequency, the most handy high frequency, thus form high rigidity and low-loss film easily, but can cause layer thickness profile with too high frequency.For film-forming temperature, can with conventional membrance casting condition same range as in temperature under carry out film forming.If under too high temperature, form this film, can cause the arrowband, cause that loss increases, and therefore, had better not be provided with De Taigao to temperature.

Therefore, the numerical value in each value and the conventional membrance casting condition does not have too big difference.Yet, think that spin density and spin depend on the film forming parameter slack time widely, so that can not form accurate film with good repeatability so far.

The following describes concrete film forming procedure.

Slowly open some necessary outflow valves and auxiliary valve 2260 in valve 2251～2256, by gas transmission pipeline 2114, from gas cylinder 2221～2226 source gas that superficial layer is required CH for example ₄Gas and H ₂Pneumatic transmission is gone into reaction chamber 2110.Then, operations flows amount controller 2211～2216 is regulated each source gas it is flowed by set rate.Under the sort of situation, the branch (divergence) that regulates main valve 2118 observes vacuum gauge 2119 simultaneously, makes the pressure in the reaction chamber 2110 reach the predetermined pressure that is not higher than 1 torr.When the internal pressure change is stablized, by predetermined power source high frequency electric source 2120 is set, by high frequency matching box 2115 it is supplied with negative electrode, so produce the high frequency glow discharge.The source gas of sending into reaction chamber 2110 decomposes because of the discharge energy that produces like this, thereby forms the predetermined illuvium that mainly is made of silicon on cylindric substrate for film deposition 2112.After the film that forms predetermined thickness, stop the supply high frequency power supply, to close and flow out valve 2251～2256, the source gas of making stops to flow into reaction chamber 2110.So just, finished the formation of photoconductive layer.

In film forming procedure, cylindric substrate for film deposition 2112 is rotated with initial velocity with the drive system (not shown).When requiring film that high like this hardness is arranged, also available low-pass filter (not shown) adds the DC bias voltage to high frequency electric source.

In order to improve the release performance of superficial layer more, to carrying out fluorination treatment or fluorination treatment is carried out in the corrosion of the plasma that forms by the gas that decomposes contain fluorine atoms in its surface.When fluoridizing,, then can obtain effect of the present invention as long as spin density and spin relaxation time satisfy regulation of the present invention with fluoro plasma.When fluoridizing, by appropriate value be provided with gases used kind with mixing ratio, become film pressure, high frequency electric source and its frequency, processing time etc., this and do not mean that any other the equipment of any needs.The plasma enhanced CVD system of available any routine carries out surface treatment.

Specifically, the fluoro-gas of Shi Heing for example is: CF ₄, CH ₃F, CH ₂F ₂, CHF ₃, C ₂F ₄, C ₂H ₃F, CIF ₃, SF ₆, HF and F ₂, and when forming plasma, can produce any gas that activity is fluoridized base.In use, available weighing apparatus outgas body dilutes these.As trend, having under the gas situation of deep-etching performance, preferably they dilute them in large quantities.

As for processing pressure, be set to pressure with conventional membrance casting condition same range as.Can be different according to gaseous species, cannot say utterly.Because shaggy possibility increases, too low in some cases pressure is also bad.As for high frequency electric source, unless the discharge energy that is higher than certain level is provided, c h bond closes can not be cut off and can not form and fluoridizes base.If too high discharge energy is provided on the other hand,, produce dangling bonds, so also bad because of possibility corrosion damage surface.When with coaxial circles tubular film forming stove, the power that is lower than about 2000W is better.

The schematically illustrated device instance of producing photosensitive part (electronic photographic photosensitive component) by the embodiment different of Fig. 3 with Fig. 2.Fig. 3 schematically shows the part sectioned view of this equipment reaction chamber and a substrate part.

In Fig. 3, label 300 expression deposition systems; The 301st, the reaction chamber that it can keep vacuum atmosphere so is set.Label 302 is illustrated in its end to sweeping the gas outlet of answering chamber 301 inside openings, and the other end of this gas outlet links to each other with the exhaust system (not shown).The discharge space that label 303 expressions are surrounded by a plurality of cylindric substrate for film deposition 304.High frequency electric source 305 links to each other with electrode 307 by high frequency matching box 306.Each cylindric substrate for film deposition 304 all around 309 configurations of rotation displacement axle, is placed on carriage 308 (a) and 308 (b) simultaneously.They are set like this, so that be rotated with motor 310 when needed.

The available system identical with system shown in Fig. 2 is as source gas delivery system (not shown).Each component gas mixes, and sends into reaction chamber 301 with gas transmission pipeline 311 by valve 312.

As long as can produce be applicable in 10W～5000W scope or more than the output power of the equipment used, the high frequency electric source that so just can use the power supply of any output to use do the present invention.As for high frequency electric source output pulsation degree, can be any value that obtains effect of the present invention.

Only can make high frequency electric source 305 and load matched, the matching box that can use any structure is as high frequency matching box 306.As the method for coupling, can automatically control, or artificially control, and to the present invention without any negative interaction.

The combination of available copper, aluminium, gold, silver, platinum, lead, nickel, cobalt, iron, chromium, molybdenum, tantalum, stainless steel and two or more these materials is as the material that applies the electrode 307 of high frequency electric source.Electrode preferably has cylindrical shape, can select ellipse or polygon.Preferably make electrode shape and substrate 304 that shape is set is consistent.

Electrode 307 can dispose cooling device arbitrarily.As concrete cooling device, can select water, air, liquid nitrogen, peltier device to wait cooling electrode as required.

As mentioned above, cylindric substrate for film deposition 304 can be made of any material, according to its application Any shape can be arranged.

The structure of the schematically illustrated equipment of Fig. 4 is used to illustrate that carrying out image with electronic photographing device forms the example of handling, and wherein electronic photographing device is as the image forming apparatus that utilizes electrostatic imaging.Along arrow directions X rotation photosensitive part 401.Around photosensitive part 401 following parts are set: main charger 402, electrostatic latent image forms part 403, developer 404, offset medium induction system 405, transfer printing charging device 406 (a), separation of charged device 406 (b), clearer 407, induction system 408 is eliminated electric charge light source 409, delivery track 419 etc.

Specifically describe image below and form the example of handling.With the main charger 402 that is added with high pressure electrostatic charging photosensitive part 401 equably.Electrostatic latent image at photosensitive part forms part, that is to say on the part of being throwed and form electrostatic latent image by emission light from projecting lamp 410, from being arranged at source 412 reflections on the source glass plate 411, by level crossing 413,414 and 415, lens 418 with scioptics unit 417 form image, derive by level crossing 416 then.To this latent image, carry toner from developer 404 with negative polarity, form the toner image.

Simultaneously, transmit offset medium P along the direction of photosensitive part 401, and regulate its forward position part with resist roller 422 and carry regularly with offset medium induction system 405.Gap between transfer printing charging device 406 (a) and photosensitive part 401 provides the positive electric field that has with the toner opposite polarity to the offset medium P at its back side.Offset medium P is given in the picture transmission of the negative polarity tone that forms on unwise parts surface as a result.Then, utilize the curvature of photosensitive part selectively, by the separating charger 406 (b) that is added with high voltage AC offset medium P is separated with photosensitive part 401, the offset medium P with static image is from this equipment output.

Collect the toner that is retained on the photosensitive part 401 with magnetic roller 427 and the cleaning spade 421 that is arranged at cleaning unit 407, and the electrostatic latent image that keeps is by eliminating 409 releases of electric charge light source.Label 420 expression blanking exposure light sources, it is to remove electric charge for the surface portion from photosensitive part 401 that this light source is set, making on the unauthorized zone of photosensitive part 401 does not have toner.

Example

Further specify the present invention with the example of listing below.

(example 1)

Use the plasma enhanced CVD system that Fig. 2 went out, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base, and under condition shown in the table 2, form superficial layer thereon in proper order.Wherein, change the flow velocity and the high frequency electric source of hydrogen, produce five photosensitive part A～E, its superficial layer has different spin densities and spin relaxation time.The spin density of each film that forms and spin relaxation time value are as shown in table 6.

Table 1

Be used to produce the condition of photosensitive part

(following restraining barrier, photoconductive layer)

Following restraining barrier

SiH ₄ 260sccm

H ₂ 500sccm

NO 7sccm

B ₂H ₆ 2100ppm

Power 110w

Internal pressure 0.43 torr

Layer thickness 1.5 μ m

Photosensitive layer

SiH ₄ 510sccm

H ₂ 450sccm

B ₂H ₆10ppm is (with SiH ₄Ratio)

Power 450w

Internal pressure 0.55 torr

Layer thickness 20 μ m

Table 2

Be used to form the condition of superficial layer

(example 1, comparative example 1)

CH ₄ 100sccm

H ₂Variable

Power variable

Frequency 13.56MHz

Internal pressure 0.4 torr

Layer thickness 0.1 μ m

Do the test in serviceable life of duplicating machine with five drums of aforesaid way preparation with a certain intensity its surface that mechanically rubs, after this, the performance after estimating it and being installed in long-time use on the duplicating machine.At first, process speed going barrel with 400mm/sec, the polishing SiC band (LT-C2000 that average particulate diameter (8 μ m) is arranged, can be from Fuji Photo Fim Co., Ltd. buy) be substantially equal to part that toner is in contact with it, hold down the parallel pivot of 3mm diameter and 20mm width then, thereby the friction drum is surperficial under load application.And always the speed with 1mm/sec moves sand belt, so that always carry undressed zone, keeps polishing force constant, the negative interaction that does not have polishing tail to produce in addition.Stressed friction was like this carried out 80 minutes.

Each five drum that prepare like this is contained on the modified machine of the NP6062 duplicating machine of being made by CANON INC..The test resolution of buying from CANON INC. (trade mark numbering: FY9-9058) be positioned on the glass plate, under common exposure, duplicate 10000 A4 paper.Wherein, use mean grain size be the toner of 8 μ m as toner, as cleaning spade, its pressure is provided with to such an extent that be lower than the pressure of conventional shovel with the cleaning spades of common low 4 degree of cleaning spade of JIS hardness ratio, so that duplicate will causing under the bonding environment of fusing.After duplicating 10000, to two kinds of images: (the trade mark numbering: FY9-9042) image of Fu Yining is estimated for image that duplicates from test resolution and the shadow tone chart of buying from CANON INC..It is bonding whether inspection melts, and afterwards, takes out drum its surface condition of microscopic examination, and checking is having visual position the bonding incident of fusing of any trace whether to occur.

The test result that obtains by above-mentioned evaluation shown in the table 6.

(comparative example 1)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base, deposition surface layer thereon then.Wherein, with condition identical shown in the table 2 under form superficial layer, just so change the flow velocity and the high frequency electric source of hydrogen, be formed with the spin density outside the scope of the invention and the superficial layer of spin relaxation time.Generate photosensitive part F and G like this.Its spin density and spin relaxation time value are as shown in table 6.

Then, to these photosensitive parts do with example 1 in identical evaluation.

Table 6 is illustrated in the check result of any variation on the performance with result in the table 1.

In the image that after evaluation is duplicated 10000, forms, in photosensitive part F, find to deceive to stop the shape sign, although very little.In photosensitive part G, discovery is cleaned the horizontal line that produces by error code and is thought because of melting the black line of bonding generation.In all examples that use other photosensitive part, do not find the bonding influence of fusing of image.

Each drum is taken out duplicating machine, use microscopic examination.As a result, in all photosensitive part A～E of the scope of the invention, do not find the bonding sign of fusing, and in photosensitive part F and G, find the bonding sign of fusing.Especially, find that photosensitive part G is consistent with the bonding contamination of fusing that image upward occurs along the sign of drum sense of rotation growth.

By example 1 and comparative example as can be known, spin density and spin relaxation time must be lower than 1 * 10 respectively ²⁰Commentaries on classics/cm ³With 10 ^-2Second.

(example 2)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base.Then, use plasma enhanced CVD illustrated in fig. 2 system, deposition surface layer under condition shown in the table 3, wherein, hydrogen flow rate and high frequency electric source be set to appropriate value with in superficial layer in conjunction with fluorine atom, thereby form photosensitive part H.In addition, in condition shown in the table 2 be provided with after hydrogen flow rate and high frequency electric source be appropriate value deposition surface layer, under the condition that is used to fluoridize as shown in table 4, the photosensitive part surface is exposed to fluoro plasma, to fluoridize.Wherein, processing list surface layer under such condition makes superficial layer have the spin density in the scope of the invention and the relaxation time that spins.Spin density and spin relaxation time value are as shown in table 7.

Test these drums with the mode identical with example 1, with polish test and estimate improve duplicate whether melt in the machine bonding.Afterwards, measure the fluorine amount of test front and back, with the retention of evaluation fluorine atom and the proper proportion of its original bulk.Measure the fluorine amount with the sub-mass spectrometry of X-ray photoelectric (XPS), to measure the very fluorine amount on close surface (about 50 dusts of the degree of depth).The result represents with the ratio of initial value with the value after testing.

The test result that obtains by above-mentioned evaluation shown in the table 7.

(comparative example 2)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base.Then, use Fig. 2 to go out the plasma enhanced CVD system, under condition shown in the table 3, form in the film superficial layer in conjunction with fluorine atom, thus formation photosensitive part J.In addition, under condition shown in the table 2, after the deposition surface layer, under the condition that is used to fluoridize as shown in table 4, the photosensitive part surface is exposed to fluoro plasma, fluoridizing, thereby finishes photosensitive part K.Wherein, processing list surface layer under such condition is so that superficial layer has spin density and spin relaxation time outside the scope of the invention.Spin density and spin relaxation time value are as shown in table 7.

Then, to the photosensitive part of preparation do with example 2 in identical evaluation.

The test result of Huo Deing result in example 2 is illustrated in the table 7 like this.

Under the situation of photosensitive part H that uses the scope of the invention and I, on image and drum, all do not find the bonding sign of fusing.When measuring the fluorine amount,, find that photosensitive part H and I have respectively for making about 80% and about 75% fluorine amount retention of back fluorine amount even after test.

On the other hand, using under photosensitive part J and the K situation (comparative example 2), on image, find to think because of melting the bonding stain that produces, even very little.Find also that on drum fusing is bonding.As measuring fluorine amount result, make fluorine atom that the back exists be reduced to test respectively before the fluorine amount about 20% and about 15%.In this case, think that polishing (polishing) causes vicious cycle, lip-deep fluorine atom is come off, dangling bonds increase, and dangling bonds then make friction force become big, cause melting bonding generation, even very light.

By example 2 and comparative example 2 as can be known, even for improving release performance and the smooth fluorine atom of introducing, but only form film or processing like this, just can keep desired effects when being controlled within the scope of the invention with the spin relaxation time to spin density, when they outside the scope of the invention time, just can not obtain such effect.

(example 3)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit sequentially on the cylindric aluminium base.Then, use Fig. 3 to go out the plasma enhanced CVD system, deposition surface layer under condition shown in the table 5, wherein, use three kinds: 50,100 and the 200MHz discharge frequency, it is that appropriate value is selected membrance casting condition with this that hydrogen flow rate and high frequency electric source are set, so that spin density and spin relaxation time are controlled within the scope of the present invention.Thereby make photosensitive part L, M and N.

Then, use the mode identical to test these parts, polish test and melt bonding evaluation with example 1.

The test result that obtains shown in the table 8.By this result and example 1 (discharge frequency: 13.56MHz) as can be known, can prepare the photosensitive part that can obtain effect of the present invention, and no matter high frequency electric source oscillation frequency and be used to form the difference of the equipment of superficial layer.

Table 3

Be used to form the condition of superficial layer

(example 2, comparative example 2)

CH ₄ 100sccm

CF ₄Variable

Power variable (800～1200W)

Frequency 13.56MHz

Internal pressure 0.3 torr

Layer thickness 0.1 μ m

Table 4

The fluoro plasma condition

(example 2, comparative example 2)

CF ₄Variable

Power variable (800～1200W)

Frequency 13.56MHz

Internal pressure 0.6 torr

Table 5

Be used to form the condition of superficial layer

(example 3)

CH ₄ 100sccm

H ₂Variable

Power variable

Changeable frequency (50,100,200MHz)

Internal pressure 2mT torr

Layer thickness 0.1 μ m

Table 6

With accelerated test to melting bonding evaluation

When spin density spin is lax to the microscope surface of image

(rotation/cm ³) between (sec) influence observe example 1:

A 8.7E18 5.2E-3 A A

B 1.5E19 6.8E-3 A A

C 3.6E19 7.2E-3 A A

D 5.4E19 8.5E-3 A A

E 8.9E19 9.2E-3 A A comparative example:

F 1.8E20 2.6E-2 B B

G 2.1E20 5.7E-2 C C is to the influence of image: A: to melting bonding nothing influence.B: visible small stain.C: as seen melt bonding wire sign.Microscope surface observation: A: it is bonding not have fusing.B: visible small fusing is bonding.C: the fusing of visible growth is bonding.

Table 7

To the evaluation of fluorophor under different condition

(1) (2) fluorophor quality when the spin density spin is lax: pre-

(rotation/cm ³) between (sec) test/back power of the test example 2:

H 2.7E19 5.5E-3 A A 80％

I 5.3E19 7.1E-3 A A 75% comparative example 2:

J 1.5E20 3.1E-2 B B 20％

K 3.7E20 4.8E-2 B C 15% (1) influence: A: to melting bonding nothing influence to image.B: visible small stain.C: as seen melt bonding wire sign.(2) microscope surface observation: A: it is bonding not have fusing.B: visible small fusing is bonding.C: the fusing of visible growth is bonding.

Table 8

Evaluation under the different high frequency power conditions

Frequency is to the microscope surface of image

(MHz) influence is observed

Example 3:

L 50 A A

M 100 A A

N 200 A A

Influence to image:

A: to melting bonding nothing influence.

B: visible small stain.

C: as seen melt bonding wire sign.

The microscope surface observation:

A: it is bonding not have fusing.

B: visible small fusing is bonding.

C: the fusing of visible growth is bonding.

(example 4)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base, then, deposition surface layer thereon.Deposition surface layer under condition shown in the table 2, but change hydrogen flow rate and high frequency electric source to form superficial layer under the condition identical with example 1, makes spin density and spin relaxation time within the scope of the present invention.Thereby make photosensitive part 0.

Then, use the drum do not include with the test machine of duplicating machine identical layer, measure drum sensitivity.With the process speed going barrel of 400mm/sec, and operation corona degree electrical equipment, so that give the charge potential of the about 400V in surface.After this, change exposure in exposure portion, at development position surface measurements current potential.Wherein, the exposure when surface potential is 50V is expressed as sensitivity.With the remolding sensitivity of conventional superficial layer, estimate this sensitivity.

Then, use the above-mentioned drum that does not comprise test machine, the variation of surface measurements current potential under contingent condition.For foundation ghost image current potential judges, change the drum surface, then, after it is through a circulation identical with duplicating processing such as exposure, electric charge eliminations, provide the shadow tone current potential, wherein, observe the potential difference (PD) between exposure area and the unexposed area and obtain this value.Whether there is problem to judge to when calculating potential difference (PD), especially using as image.

For checking the poor of disruptive strength, use the modified machine of NP6062, remove the grid of halation charger, a little higher than charge position of desiring to cause the environment of releasing that is used to set up is set.Use such improvement machine to duplicate, compare at the image of starting stage and image after duplicating 1000, wherein, the image quantity that blank defects is arranged on white (white point) that counting causes because of releasing.Estimate the comparison of this quantity that expression is obtained when conventional superficial layer is made same test as for it.

To the evaluation of sensitivity, to the evaluation of ghost image current potential and to the defect picture that causes because of releasing evaluation obtained the results are shown in the table 9.

(comparative example 3)

Use plasma enhanced CVD illustrated in fig. 2 system, under condition shown in the table 1, restraining barrier and photoconductive layer under deposit on the cylindric aluminium base, then, deposition surface layer thereon.Under condition shown in the table 2, form superficial layer, but change hydrogen flow rate and high frequency electric source,, make spin density and spin relaxation time outside the scope of the invention under the condition identical, to form superficial layer with comparative example 1.Thereby make photosensitive part P.

Then, use the mode identical to judge with example 4.

Table 9 is represented the result of acquisition like this with the result of table 4.

Table 9

The evaluation of sensitivity and disruptive strength

Sensitivity ghost image disruptive strength when the spin density spin is lax

(rotation/cm ³) between (sec) * * *

Example 4:

O 2.4E19 5.8E-3 AA AA AA

Comparative example 3:

P 1.6E20 2.4E-2 A A A

* compare with routine

AA: fine

A: on conventional levels

B: no problem in the time use

C: under some situation problem is arranged in actual the use

In comparative example 3, estimate its result with respect to the conventional superficial layer that constitutes by SiC.On the other hand, in the example 4 within the scope of the present invention, find that the sensitivity of the conventional superficial layer of remolding sensitivity reduces less.This is unexpected result, and estimation may be because underlying cause: because of dangling bonds reduce, thereby the contributive atom of para-linkage reduces, thereby causes whole bonding force to increase, and makes the bands of a spectrum crack bigger, reduces in the loss of superficial layer.

In the evaluation of relevant ghost image current potential, the comparative example 3 outside the scope of the invention illustrates the result identical with conventional photosensitive part.On the other hand, the ghost image current potential of finding example 4 within the scope of the present invention is less than this current potential of conventional photosensitive part and be difficult to take place ghost phenomena.Only can not explain its reason with the superficial layer of several thousand dust thickness at the most, also unclear at present.

In the test of voltage breakdown duration, find that the comparative example 3 outside the scope of the invention has the result identical with conventional photosensitive part.On the other hand, the white point of discovery example 4 within the scope of the present invention less changes.As the surperficial fractographic result of drum who does after test, in comparative example 3, observation is released, and takes place at the edge of peripheral outshot, and in example 4, almost can not observe the sign of releasing at peripheral outshot.Estimate this difference be because: cover well within the scope of the present invention the on-monocrystalline carbon film and the improvement of film compactness.As a result, think that disruptive strength is enhanced.

As mentioned above, according to the present invention, with low spin density and spin relaxation time being arranged and comprising that at least the on-monocrystalline carbon film of hydrogen atom forms surface region (layer), so that improve the release performance and the smooth property of toner.Like this, present invention can be implemented under every kind of environment that no toner melts bonding and very long-life photosensitive part is arranged on drum comes to the surface.

The present invention also can realize such photosensitive part, and high sensitivity is promptly arranged, and causes ghost phenomena hardly, does not produce any defect picture that has of releasing and causing because of surface charge, and can stably obtain not cause in time the high quality image of any change.

Claims

1. a photosensitive part comprises electrically-conductive backing plate, is arranged at the photoconduction district on the substrate and is arranged at the surface region that photoconduction is distinguished;

2. photosensitive part according to claim 1 is characterized in that the spin density of on-monocrystalline carbon film is equal to or less than 1 * 10 ²⁰Spin/cm ³, the spin relaxation time is equal to or less than 10 ^-2Second.

3. photosensitive part according to claim 1 is characterized in that, comprises fluorine atom in the film of on-monocrystalline carbon film.

4. photosensitive part according to claim 3 is characterized in that the surface of on-monocrystalline carbon film or near surface have the fluoro-carbon bond.

5. photosensitive part according to claim 1 is characterized in that also comprising: have zone of transition between photoconduction district and surface region, its component is the intermediate between this two district.

6. photosensitive part according to claim 1 is characterized in that, photoconduction district and surface region have photoconductive layer and superficial layer respectively.

7. photosensitive part according to claim 3 is characterized in that, forms surface region with the source gas that comprises fluorine atom.

8. photosensitive part according to claim 7 is characterized in that, the source gas that comprises fluorine atom comprises CF ₄Gas.

9. photosensitive part according to claim 1 is characterized in that, the plasma enhanced chemical vapor deposition of the high frequency by using 1MHz～450MHz forms surface region.

10. photosensitive part according to claim 9 is characterized in that described high frequency is in the scope of 50MHz～450MHz.

11. photosensitive part according to claim 1 is characterized in that, the photoconduction district comprises the non-single-crystal material that mainly is made of silicon atom.

12. photosensitive part according to claim 1 is characterized in that, the on-monocrystalline carbon film comprises amorphous carbon-film.

13. an image processing system comprises:

Photosensitive part comprises electrically-conductive backing plate, is arranged at the photoconduction district on the substrate and is arranged at the surface region that photoconduction is distinguished; With low spin density and the spin relaxation time of lacking being arranged and comprising that at least the on-monocrystalline carbon film of hydrogen atom forms surface region;

Charger is used for the photosensitive part surface electrostatic is charged;

Light source is used for the photosensitive part face exposure;

Developer is used for providing toner according to the electric charge that keeps from the teeth outwards to the photosensitive part surface;

Transfer device is used for the toner that the photosensitive part surface is supplied with in transfer printing;

Clearer is used to clean photosensitive parts surface;

14. image processing system according to claim 13 is characterized in that, the spin density of on-monocrystalline carbon film is equal to or less than 1 * 10 ²⁰Spin/cm ³, the spin relaxation time is equal to or less than 10 ^-2Second.

15. image processing system according to claim 13 is characterized in that, comprises fluorine atom in the film of on-monocrystalline carbon film.

16. image processing system according to claim 15 is characterized in that, the surface of on-monocrystalline carbon film or near surface have the fluoro-carbon bond.

17. image processing system according to claim 13 is characterized in that also comprising: have zone of transition between photoconduction district and surface region, its component is the intermediate between this two district.

18. image processing system according to claim 13 is characterized in that, photoconduction district and surface region have photoconductive layer and superficial layer respectively.

19. image processing system according to claim 15 is characterized in that, utilizes the source gas that contains fluorine atom to form surface region.

20. image processing system according to claim 19 is characterized in that, the source gas that comprises fluorine atom comprises CF ₄Gas.

21. image processing system according to claim 13 is characterized in that, the plasma enhanced chemical vapor deposition of the high frequency by using 1MHz～450MHz forms surface region.

22. image processing system according to claim 21 is characterized in that, described high frequency is in the scope of 50MHz～450MHz.

23. image processing system according to claim 13 is characterized in that, the photoconduction district comprises the non-single-crystal material that mainly is made of silicon atom.

24. image processing system according to claim 13 is characterized in that, the on-monocrystalline carbon film comprises amorphous carbon-film.

25. image processing system according to claim 13 is characterized in that clearer has scraper plate.

26. an image forming method comprises the following steps:

Photosensitive part exposure to charging;

Form the toner image on the photosensitive part surface according to exposure;

Transfer printing toner image; With

After transfer printing toner image, clean photosensitive parts surface.

27. image forming method according to claim 26 is characterized in that, the spin density of on-monocrystalline carbon film is equal to or less than 1 * 10 ²⁰Spin/cm ³, the spin relaxation time is equal to or less than 10 ^-2Second.

28. image forming method according to claim 26 is characterized in that, comprises fluorine atom in the film of on-monocrystalline carbon film.

29. image forming method according to claim 28 is characterized in that, the surface of on-monocrystalline carbon film or near surface have the fluoro-carbon bond.

30. image forming method according to claim 26 is characterized in that also comprising: have zone of transition between photoconduction district and surface region, its component is the intermediate between this two district.

31. image forming method according to claim 26 is characterized in that, photoconduction district and surface region have photoconductive layer and superficial layer respectively.

32. image forming method according to claim 26 is characterized in that, utilizes scraper plate to clean.

33. image forming method according to claim 26 is characterized in that, exposure comprises blank exposure.

34. image forming method according to claim 26 is characterized in that, repeats each step in proper order according to it.

35. a method for preparing photosensitive part comprises the following steps:

Atmosphere under the decompression state in the chamber that can be evacuated and have substrate is applied energy, and this atmosphere comprises carbon atom and hydrogen atom, and forms the photoconduction district on this substrate; With

36. the method for preparing photosensitive part according to claim 35 is characterized in that the spin density of on-monocrystalline carbon film is equal to or less than 1 * 10 ²⁰Spin/cm ³, the spin relaxation time is equal to or less than 10 ^-2Second.

37. the method for preparing photosensitive part according to claim 35 is characterized in that, comprises fluorine atom in this atmosphere.

38., it is characterized in that, by CF according to the described method for preparing photosensitive part of claim 37 ₄Gas is sent into fluorine atom.

39. the method for preparing photosensitive part according to claim 35 is characterized in that, uses the high frequency of 1MHz～450MHz to produce plasma.

40., it is characterized in that described high frequency is in the scope of 50MHz～450MHz according to the described method for preparing photosensitive part of claim 39.