CN100545757C - Electrophtography photosensor - Google Patents
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- CN100545757C CN100545757C CNB2007101050614A CN200710105061A CN100545757C CN 100545757 C CN100545757 C CN 100545757C CN B2007101050614 A CNB2007101050614 A CN B2007101050614A CN 200710105061 A CN200710105061 A CN 200710105061A CN 100545757 C CN100545757 C CN 100545757C
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Abstract
Electrophtography photosensor of the present invention, have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on the optical conductive layer with silicon atom and carbon atom non-single crystalline layers as parent, on being stacked in optical conductive layer with silicon atom and carbon atom as the thickness direction in the non-single crystalline layers zone of parent, the amount of the oxygen atom of constituting atom total amount distributes and has peak value relatively.
Description
The present patent application be submitted on July 30th, 2004, denomination of invention divides an application for the 200410058868.3rd the patent application of " Electrophtography photosensor ".
Technical field
The present invention relates to that the such electromagnetic wave of light (be the light of broad sense, refer to ultraviolet ray, luminous ray, infrared ray, X ray, gamma-rays etc.) is had the Electrophtography photosensor of sensitivity.
Background technology
So far, light conductive material as the optical conductive layer that forms Electrophtography photosensor, require highly sensitive, SN is higher than [photocurrent (Ip)/dark current (Id)], have the absorption spectrum of the spectral characteristic that is suitable for irradiates light, harmless when using again, express the amorphous silicon (also souvenir is a-Si) of remarkable character in this respect, particularly hydrogenated amorphous shape silicon (also souvenir is a-Si:H) extensively is used.
The light conductive material that this a-Si is, in general, be by conductive base being heated to 50 ℃～350 ℃, on this matrix, form with the one-tenth embrane method of vacuum evaporation method, sputtering method, ion plating, hot CVD method, optical cvd method, plasma CVD method etc.Wherein plasma CVD method promptly decomposes unstrpped gas by high frequency or microwave glow discharge, and the method that forms the a-Si:H accumulating film on matrix is suitable, is widely used.
In recent years, be accompanied by the digitizing with article and image popularized that computing machine enters office and general family, also be digitized, form sub-image by light source and becoming main flow based on single wavelength as the electro-photography apparatus of output unit.On the other hand, in order to improve picture characteristics, optical exposure device in the electro-photography apparatus, developing apparatus, transfer device etc. are improved, and the result is even if tried to achieve the method that also picture characteristics can be improved higher than prior art in Electrophtography photosensor.
Existing Electrophtography photosensor, in order to reach the dark resistance that improves photoconduction electricity parts with the optical conductive layer that constitutes by the a-Si accumulating film, luminous sensitivity, optical Response etc., light, the environment for use characteristic of the characteristic of photoconduction electricity and moisture-proof etc., the purpose of further time stability, for example, as spy clear in Japan and that announced in 57 years open put down in writing in the clear 57-115556 patent gazette, by on by the optical conductive layer that silicon atom is constituted as the amorphous material of mother metal, setting obtains the potential property of charged ability and luminous sensitivity brilliance by the surperficial barrier layer that the amorphous material of the non-photoconductivity that comprises silicon atom and carbon atom constitutes.
Again, as put down in Japan the spy who announced in 6 years open put down in writing in flat 6-242623 patent gazette (USP5556729), by between negative charging is with the optical conductive layer of Electrophtography photosensor and superficial layer with amorphous silicon as main body, and contain less than the boron of 50 atom ppm or do not comprise the positive hole trapping layer of arranging conductive element, obtain remarkable electrofax characteristic.
Again, as put down in Japan the spy who announced in 11 years open put down in writing in flat 11-242349 patent gazette (USP6238832), by in the superficial layer of Electrophtography photosensor, all containing oxygen, nitrogen, fluorine, boron atom at least simultaneously, can not peel off, damage and wear away between long-term, using, can access the high Electrophtography photosensor of electrical characteristics preferable image quality.
According to technical progress as described above, can realize good electron photosensitive body, but require more high-quality Electrophtography photosensor the today of the product requirements level that produces being increased day by day in market.
Particularly, in recent years, in universal unusual significant digital and electronic photographic means and digital full color electronic photographing device, original copy for type composition not only, and duplicating of photo, drawing, design drawing etc. also become very frequent, so require the repeatability of point is brought up to more than the prior art.For example, when the point that makes image is little at interval, when reaching high image resolution, there is the unstable situation that the image flow phenomenon takes place of some repeatability.Again simultaneously, as requiring the more problem of high image qualityization, further requiring with the afterimage is the optical storage and the raising sensitivity of representative.
In order to solve these problems, as mentioned above, implement the optimization of the layer formation of digit explosure, membranous improvement and the control of element amount, but market is very high to the requirement of image level as mentioned above, wish to improve more picture characteristics consumingly.In recent years, the Electrophtography photosensor that is requiring to be used for the digital and electronic photographic means has the above permanance of prior art, but when the countermeasure as it increased the thickness of superficial layer, the charged carriers that forms sub-image spread to transverse direction easily.Therefore, have the unsettled situation of some repeatability, strong hope has the technology of control charged carriers to the transverse direction diffusion.
Again, in digital full color electronic photographing device, the most general combination as charged, development etc., be considered as color toner, the negative toner that the material range of choice is wide, the controlled height of sub-image, be suitable for the image exposure method (making the method for image section exposure) of high image qualityization, at this moment, need make the photoreceptor belt negative charge.In digital full color electronic photographing device, because being photoreceptor always, the a-Si of the electronegative usefulness of considering so far is merely able to stop negative charge to inject from the surface, inject the restraining barrier so wish to be provided with the top electric charge, how improving this top electric charge is injected silicon atom that the restraining barrier also comprises and the carbon atom non-single crystalline layers zone as parent, is the key that improves characteristic.
Particularly, for in recent years to the requirement of digital full color duplicating machine, the photoreceptor characteristic synthetically need be brought up to more than the photoreceptor so far, for example, exist as 1 treatment conditions, in order around Electrophtography photosensor, a plurality of developers to be set, with large-scale developing parts, the formation that the distance from charged device to developer is left easily.Therefore, descend in order to compensate the current potential from charged device to developer that is caused by dark decay, charged current potential need be brought up to more than the charged current potential so far, the importance that the top electric charge injects the restraining barrier has more and more increased.
Summary of the invention
The purpose of this invention is to provide the superior high-quality Electrophtography photosensor of picture characteristics.That is, provide and to improve a repeatability and improve charged ability, further can reach the Electrophtography photosensor that reduces optical storage and improve the effect of sensitivity.
In order to achieve the above object, the invention provides Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises oxygen atom, thickness direction in this non-single crystalline layers zone, the amount of the oxygen atom of constituting atom total amount distributes and has peak value relatively.
Again, the invention provides Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises fluorine atom, thickness direction in this non-single crystalline layers zone, the amount of the fluorine atom of constituting atom total amount distributes and has peak value relatively.
Further, the invention provides Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises oxygen atom and fluorine atom, thickness direction in this non-single crystalline layers zone, the amount of the relative constituting atom total amount with fluorine atom of oxygen atom distribute and have peak value.
Description of drawings
Figure 1A, 1B, 1C and 1D are the pattern sectional views that is used to illustrate the example of Electrophtography photosensor of the present invention.
Fig. 2 is the mode declaration pattern specification figure of an example of the manufacturing installation of expression Electrophtography photosensor of the present invention.
Fig. 3 is the oxygen atom of explanation in the superficial layer of the present invention and the example of the depth section figure of the peak value of fluorine atom amount.
Fig. 4 is an example of the peak half width in the explanation superficial layer of the present invention.
Fig. 5 is the mode declaration pattern specification figure of an example that expression is provided with the digital and electronic photographic means of Electrophtography photosensor of the present invention.
Fig. 6 be expression of the present invention for electronegative with Electrophtography photosensor with silicon atom and carbon atom figure as an example of the distribution of the carbon atom amount of the thickness direction in the non-single crystalline layers zone of parent.
Fig. 7 be expression of the present invention for electronegative with Electrophtography photosensor with silicon atom and carbon atom figure as an example of the distribution of the amount of the carbon atom amount of the thickness direction in the non-single crystalline layers zone of parent and belonging to group 13 of periodic table element.
Fig. 8 be expression of the present invention for electronegative with Electrophtography photosensor with silicon atom and carbon atom figure as other example of the distribution of the amount of the carbon atom amount of the thickness direction in the non-single crystalline layers zone of parent and belonging to group 13 of periodic table element.
Fig. 9 be expression of the present invention for electronegative with Electrophtography photosensor with silicon atom and carbon atom figure as another other example of the distribution of the amount of the carbon atom amount of the thickness direction in the non-single crystalline layers zone of parent and belonging to group 13 of periodic table element.
Embodiment
Present inventors have carried out investigation with keen determination in order to achieve the above object, and the result finds that control is stacked on the optical conductive layer silicon atom and carbon atom can be produced very big influence to picture characteristics as the composition in the non-single crystalline layers zone of parent.Further, present inventors find by so that be stacked in and on the optical conductive layer silicon atom and carbon atom controlled composition as the mode that the amount of oxygen atom in the non-single crystalline layers zone of parent and/or fluorine atom has peak value, can reach and improve the some repeatability, further improve charged ability, improve and reduce optical storage and improve the such electronic photographic sensitive characteristic of sensitivity, thereby finished the present invention.
That is, the present invention is as follows.
The present invention relates to a kind of Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises oxygen atom, thickness direction in this non-single crystalline layers zone, the amount of the oxygen atom of constituting atom total amount distributes and has peak value relatively.Here, the thickness direction in the non-single crystalline layers zone is represented and the vertical face of face that constitutes layer.
It is the Electrophtography photosensor of feature that the present invention is preferably to have the zone of containing the belonging to group 13 of periodic table element in the non-single crystalline layers zone as parent with silicon atom and carbon atom on being stacked in optical conductive layer.
The present invention is preferably with in silicon atom and carbon atom are distributed as the amount of the oxygen atom of the relative constituting atom total amount in the non-single crystalline layers zone of parent on being stacked in optical conductive layer, the thickness direction in the non-single crystalline layers zone have at least 2 greatly the zone be the Electrophtography photosensors of feature.
The present invention is preferably with the thickness direction in the layer region that is present in more close optical conductive layer one side of minimal value between 2 very big zones of carbon atom amount, and having the peak value that the amount of the oxygen atom of above-mentioned relatively constituting atom total amount distributes is the Electrophtography photosensor of feature.
When the minimum amount of the oxygen atom that it is Omax that the present invention is preferably to be stacked in maximum amount in the peak value that silicon atom and carbon atom are distributed as the amount of the oxygen atom in the non-single crystalline layers zone of parent on the optical conductive layer in season, contain in above-mentioned non-single crystalline layers zone was Omin, the pass that the ratio of the minimum relatively amount Omin of maximum amount Omax satisfies 2≤Omax/Omin≤2000 was the Electrophtography photosensor of feature.Here, above-mentioned minimum amount Omin be do not comprise join with optical conductive layer and the non-single crystalline layers zone of the region of variation of lamination in minimum amount.
The present invention is preferably with in the peak value as the amount distribution of the oxygen atom in the non-single crystalline layers zone of parent with silicon atom and carbon atom on being stacked in optical conductive layer, peak half width is the Electrophtography photosensor of feature more than or equal to 10nm, smaller or equal to 200nm, and this is gratifying.
The peak value that the present invention is preferably with the amount distribution of oxygen atom does not have the Electrophtography photosensor that certain zone is a feature.
Again, the present invention relates to a kind of Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises fluorine atom, thickness direction in this non-single crystalline layers zone, the amount of the fluorine atom of constituting atom total amount distributes and has peak value relatively.
The present invention is preferably with the thickness direction in the layer region that is present in more close optical conductive layer one side of minimal value between 2 very big zones of carbon atom amount, and having the peak value that the amount of the fluorine atom of above-mentioned relatively constituting atom total amount distributes is the Electrophtography photosensor of feature.
When the minimum amount of the fluorine atom that it is Fmax that the present invention is preferably to be stacked in maximum amount in the peak value that silicon atom and carbon atom are distributed as the amount of the fluorine atom in the non-single crystalline layers zone of parent on the optical conductive layer in season, contain in above-mentioned non-single crystalline layers zone was Fmin, the pass that the ratio of the minimum relatively amount Fmin of maximum amount Fmax satisfies 2≤Fmax/Fmin≤2000 was the Electrophtography photosensor of feature.Here, above-mentioned minimum amount Fmin be do not comprise join with optical conductive layer and the non-single crystalline layers zone of the region of variation of lamination in minimum amount.
The present invention is preferably with in the peak value as the amount distribution of the fluorine atom in the non-single crystalline layers zone of parent with silicon atom and carbon atom on being stacked in optical conductive layer, and peak half width is the Electrophtography photosensor of feature more than or equal to 10nm, smaller or equal to 200nm.
The peak value that the present invention is preferably with the amount distribution of fluorine atom does not have the Electrophtography photosensor that certain zone is a feature.
Again, the present invention relates to a kind of Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent, it is characterized in that: above-mentioned non-single crystalline layers zone comprises oxygen atom and fluorine atom, thickness direction in this non-single crystalline layers zone, the amount of the oxygen atom of constituting atom total amount and fluorine atom distributes and has peak value respectively relatively.
The present invention is preferably with the thickness direction in the layer region that is present in more close optical conductive layer one side of minimal value between 2 very big zones of carbon atom amount, and having the peak value that the amount of the oxygen atom of above-mentioned relatively constituting atom total amount and fluorine atom distributes is the Electrophtography photosensor of feature.
It is each minimum amount of Omax, Fmax, the oxygen atom that contains in above-mentioned non-single crystalline layers zone and fluorine atom when being Omin, Fmin that the present invention is preferably to be stacked in each maximum amount in the peak value that silicon atom and carbon atom are distributed as the amount of oxygen atom in the non-single crystalline layers zone of parent and fluorine atom on the optical conductive layer in season, and the pass that the ratio of the minimum relatively amount Omin of maximum amount Omax, Fmax, Fmin satisfies 2≤Omax/Omin≤2000,2≤Fmax/Fmin≤2000 respectively is the Electrophtography photosensor of feature.Here, above-mentioned minimum amount Omin, Fmin be respectively do not comprise join with optical conductive layer and the non-single crystalline layers zone of the region of variation of lamination in minimum amount.
The present invention is preferably with the peak value that silicon atom and carbon atom are distributed as the amount of oxygen atom in the non-single crystalline layers zone of parent and fluorine atom on being stacked in optical conductive layer, each peak half width for oxygen atom more than or equal to 10nm, smaller or equal to 200nm, for fluorine atom more than or equal to 10nm, be the Electrophtography photosensor of feature smaller or equal to 200nm.
The peak value that the present invention is preferably with the amount distribution of oxygen atom and fluorine atom does not have the Electrophtography photosensor that certain zone is a feature.
Below, we state in detail to reach and improve the some repeatability, further improve charged ability, reduce optical storage and improve the thinking of sensitivity.
Present inventors carry out following supposition about improving the some repeatability.We think by so that on being stacked in optical conductive layer silicon atom and carbon atom are controlled composition as the mode that the amount of oxygen atom in the non-single crystalline layers zone of parent and/or fluorine atom has peak value, can prevent from effectively to form as infringement and improve a diffusion of the charged particles of the sub-image of repeatability reason, as a result, can improve a repeatability.
Again, we have distinguished that the effect that has peak value in the amount of oxygen atom and/or fluorine atom is not only the effect that improves the some repeatability, and are the charged abilities that improves Electrophtography photosensor, improve luminous sensitivity, reduce the effect that multiplies each other of optical storage.This can be envisioned as to impel by oxygen atom and the such atom of fluorine atom silicon atom and the carbon atom structure as the non-single crystalline layers of mother metal is relaxed, remove the structure defective, and further can reduce effectively owing to be present in local level's density that the structure defective in the film of working effectively as terminator terminating junctor produces.Therefore, can prevent that charged particles from by being stacked in silicon atom and carbon atom are moved as the structure defective in the non-single crystalline layers zone of parent on the optical conductive layer, making contributions to improving charged ability.Again, we imagine because can prevent from photocarrier is trapped in the local level, so can improve luminous sensitivity, reduce optical storage and combine.
Again, present inventors at length discussed oxygen atom and/or fluorine atom amount on being stacked in optical conductive layer with silicon atom and the carbon atom effect when having peak value in the thickness direction in the non-single crystalline layers zone of parent.As a result, though reason is not clear, we judge when the amount of oxygen atom has peak value, and relatively, the diffusion of charged particles is more effectively worked, and improves a some repeatability significantly when having peak value with the amount of fluorine atom.Again, we judge when the amount of oxygen atom and fluorine atom all has peak value, with when oxygen atom and fluorine atom amount separately all have peak value relatively, play the effect of the structure mitigation that makes in the non-single crystalline layers zone effectively, charged ability and luminous sensitivity can be improved significantly, further optical storage can be reduced significantly.
Further present inventors have discussed the layer formation in the diaphragm area that is stacked on the optical conductive layer, the result, we judge with to hold the negative charging usefulness Electrophtography photosensor that is stacked in the zone that silicon atom and carbon atom is contained the belonging to group 13 of periodic table element as the non-single crystalline layers zone of parent on the optical conductive layer corresponding, can improve a repeatability significantly.Though not clear now to this, whether it doesn't matter with in negative charging charged carriers being called electronics for our imagination.
Further present inventors have discussed the layer formation in negative charging is being stacked in non-single crystalline layers zone on the optical conductive layer in Electrophtography photosensor.The result, we judge the amount distribution of passing through the carbon atom of constituting atom total amount, thickness direction in the non-single crystalline layers zone has 2 greatly zones at least, thickness direction in the layer region that is present in more close optical conductive layer one side of minimal value between 2 very big zones of this carbon atom amount, the amount of the oxygen atom of constituting atom total amount is distributed in the interior thickness direction of layer region and has peak value relatively, charged ability and luminous sensitivity can be improved, further optical storage can be reduced more.Therefore, we can imagine by making silicon atom and the carbon atom structure as the non-single crystalline layers of mother metal is relaxed, and play a part to reduce effectively structure defective in the film, can improve charged ability more, will improve luminous sensitivity, and the minimizing optical storage combines.
Further present inventors at length discussed be stacked in season on the optical conductive layer with silicon atom and carbon atom as the amount of oxygen atom in the non-single crystalline layers zone of parent and/or fluorine atom and the correlativity of electrofax characteristic, the result, oxygen atom in season, maximum amount in the peak value that the amount of fluorine atom distributes is respectively Omax, Fmax, be stacked in the oxygen atom that the non-single crystalline layers zone (the above-mentioned non-single crystalline layers that does not comprise the region of variation that joins with optical conductive layer) on the optical conductive layer contains, the minimum amount of fluorine atom is Omin, during Fmin, in order to make maximum amount Omax, Fmax is to minimum amount Omin, the ratio of Fmin satisfies 2≤Omax/Omin≤2000 respectively, the relation of 2≤Fmax/Fmin≤2000, and control, except can improving a repeatability, can improve charged ability by leaps and bounds, improve luminous sensitivity, further reduce optical storage.
Further present inventors find to work as Omax 5.0 * 10
20Atom/cm
3～2.5 * 10
22Atom/cm
3, Omin is 2.5 * 10
17Atom/cm
3～1.3 * 10
22Atom/cm
3Scope in the time, again, when Fmax 5.0 * 10
19Atom/cm
3～2.0 * 10
22Atom/cm
3, Fmin is 2.5 * 10
17Atom/cm
3～1.0 * 10
22Atom/cm
3Scope in the time, again, when Omax 5.0 * 10
20Atom/cm
3～2.5 * 10
22Atom/cm
3, Omin is 2.5 * 10
17Atom/cm
3～1.3 * 10
22Atom/cm
3, Fmax is 5.0 * 10
19Atom/cm
3～2.0 * 10
22Atom/cm
3, Fmin is 2.5 * 10
17Atom/cm
3～1.0 * 10
22Atom/cm
3Scope in the time, effect of the present invention is more remarkable.
Further present inventors at length discussed be stacked on the optical conductive layer with silicon atom and carbon atom as the amount of oxygen atom in the non-single crystalline layers zone of parent and/or fluorine atom and the correlativity of electrofax characteristic, the result, we see in the peak value of the amount distribution of oxygen atom and/or fluorine atom, preferably peak half width are controlled at more than or equal to 10nm smaller or equal to 200nm.When peak half width during more than or equal to 10nm, the formation of peak value influences membrane property effectively, can improve charged ability more, improves luminous sensitivity.On the other hand, we think when peak half width during smaller or equal to 200nm, can not encumber the nearby film quality in zone of peak value, can improve a repeatability more, fully reduce optical storage.
Further present inventors at length discussed be stacked on the optical conductive layer with silicon atom and carbon atom as the peak value of the amount of oxygen atom in the non-single crystalline layers zone of parent and/or fluorine atom and the correlativity of electrofax characteristic, the result, we see so that the peak value shape does not have the mode in certain zone controls, then can not encumber nearby zone membranous of peak value, except improving some repeatability and charged ability, further can improve sensitivity fully and reduce optical storage.
If according to the present invention, then by so that be stacked in and on the optical conductive layer silicon atom and carbon atom controlled composition as the mode that the amount of oxygen atom in the non-single crystalline layers zone of parent and fluorine atom has peak value, can reach and improve the some repeatability, further improve charged ability, reducing optical storage and sensitivity increases, and improves the purpose of electrofax characteristic.
Below, we describe Electrophtography photosensor of the present invention in detail according to accompanying drawing.
Figure 1A is the pattern pie graph that is used to illustrate the layer configuration example of Electrophtography photosensor of the present invention to Fig. 1 D.
Electrophtography photosensor 100 shown in Fig. 1 D is negative charging Electrophtography photosensors, on matrix 101, sensitive layer 102 is set.Sensitive layer 102 according to the order from matrix 101 1 sides, is the bottom electric charge optical conductive layer with photoconductivity 105 that injects restraining barrier 104, constitute with a-Si:H, silicon atom and the carbon atom non-single crystalline layers zone 103 as parent is constituted by a-Si.Be to be that the 1st top electric charge middle layer 108 injecting restraining barrier 109, constitute with a-SiC:H, the a-SiC:H that constitutes with the zone of containing the belonging to group 13 of periodic table element are that the 2nd top electric charge injects restraining barrier 107 and a-SiC:H is that superficial layer 106 constitutes with silicon atom and carbon atom as the non-single crystalline layers zone 103 of parent by the a-SiC:H that constitutes with the zone of containing the belonging to group 13 of periodic table element again.Here, the dotted line in the middle layer 108 of a-SiC:H formation is the zone that forms the amount peak value of oxygen atom of the present invention and/or fluorine atom.Again, each interface of optical conductive layer 105 and electric charge injection restraining barrier 109, the 109, the 1st top, electric charge injection restraining barrier, the 1st top and middle layer 108, middle layer 108 and electric charge injection restraining barrier 107, the 107, the 2nd top, electric charge injection restraining barrier, the 2nd top and superficial layer 106 also can be to carry out interface control by the mode that region of variation inhibition boundary reflection is set.
Below, our explanation is with silicon atom and the carbon atom non-single crystalline layers zone as parent.
As Figure 1A shown in Fig. 1 D, the 103rd, be stacked on the optical conductive layer with silicon atom and carbon atom non-single crystalline layers zone as parent.Above-mentionedly silicon atom and carbon atom are injected by the top electric charge among the superficial layer among Figure 1A 106, Figure 1B as the non-single crystalline layers zone 103 of parent the 1st top electric charge that restraining barrier 107 and superficial layer 106, the middle layer 108 of Fig. 1 C, top electric charge inject restraining barrier 107 and superficial layer 106, Fig. 1 D injects restraining barrier 109, middle layer the 108, the 2nd top electric charge injects restraining barrier 107 and superficial layer 106 constitutes.
Again, the zone that forms the amount peak value of oxygen atom of the present invention and/or fluorine atom is showed by the dotted line in the middle layer 108 of the dotted line in the middle layer 108 of the dotted line in the superficial layer 106 of the dotted line in the superficial layer 106 of Figure 1A, Figure 1B, Fig. 1 C, Fig. 1 D.
Below, we describe each layer in detail.
＜superficial layer 〉
The material of the superficial layer 106 among the present invention is by silicon atom and the carbon atom non-single-crystal material as parent is formed.The carbon atom that comprises in above-mentioned superficial layer 106 both can have been implemented the even distribution that do not depart from this layer, perhaps also can be included in the state of bed thickness direction uneven distribution.But, no matter in which kind of situation, with the surperficial parallel face of matrix 101 in the direction, be included in the even distribution, from also needing for the purpose that reaches the characteristic homogenising the direction in face with not departing from.
Again, the amount of the carbon atom that comprises in above-mentioned superficial layer 106 is gratifying more than or equal to 40 atom % smaller or equal to 95 atom % for the total amount of carbon atom and silicon atom.Better more than or equal to 50 atom % smaller or equal to 90 atom %.The amount of carbon atom, it is also very high to have good antifriction consumption and sensitivity in above-mentioned scope.
Again, preferably comprise hydrogen atom in superficial layer 106, at this moment hydrogen atom compensates the not coupling key of the constituting atom of silicon etc., improves a layer quality, particularly improves photoconduction electrical characteristics and charge-retention property.From this point of view, the amount of hydrogen for the total amount of the constituting atom in the superficial layer more preferably greater than equaling 30 atom % smaller or equal to 70 atom %, better more than or equal to 35 atom % smaller or equal to 65 atom %, better more than or equal to 40 atom % smaller or equal to 60 atom %.
As the bed thickness of above-mentioned superficial layer 106, we wish usually more than or equal to 10nm smaller or equal to 5000nm, better more than or equal to 50nm smaller or equal to 2000nm, more preferably greater than equaling 100nm smaller or equal to 1000nm.When bed thickness during more than or equal to 10nm, be in the photoreceptor using a-Si, superficial layer 106 can not lose because of the reason of abrasion etc.When smaller or equal to 5000nm, can not cause because the reduction of the electrofax characteristic of the increase of residual electric potential etc. again, yet.
For the superficial layer 106 that forms the characteristic that can reach purpose of the present invention, the gaseous tension in substrate temperature, the reaction vessel need be set on the suitable value as required.Substrate temperature (Ts) is suitably selected optimum range according to layer design, but in common situation, more than or equal to 150 ℃ be gratifying smaller or equal to 350 ℃, better more than or equal to 180 ℃ smaller or equal to 330 ℃, more preferably greater than equaling 200 ℃ smaller or equal to 300 ℃.
Equally also design the optimum range of the pressure in the choice reaction vessel suitably according to layer, but in common situation more than or equal to 1 * 10
-2Pa is smaller or equal to 1 * 10
3Pa is better more than or equal to 5 * 10
-2Pa is smaller or equal to 5 * 10
2Pa is more preferably greater than equaling 1 * 10
-1Pa is smaller or equal to 1 * 10
2Pa.
In the present invention, numerical range as the hope of the substrate temperature that is used to form superficial layer 106, gaseous tension, can enumerate above-mentioned scope, but condition do not determine respectively usually independently, and the mutual and organic relevance when preferably having the photoreceptor of desirable characteristics according to formation determines optimum value.
Between superficial layer and photoconductive layer, the region of variation that changes in the mode that reduces the amount of carbon atom towards photoconductive layer can be set also again.Therefore can improve the cohesive of superficial layer and photoconductive layer, reduce the interference effect that causes by the reflection of the light on the interface more.
Further in the present invention, in the superficial layer shown in Figure 1A 106, for example the mode that has a peak value with the amount at dotted line place oxygen atom and/or fluorine atom is controlled.In order to form peak value, when forming superficial layer 106, wish to flow through the gas that is used to supply with oxygen atom and/or fluorine atom.Again, in order to be controlled at the oxygen atom that contains in the superficial layer 106 and/or the amount of fluorine atom, for example, suitably the control accumulating film formation condition of gas concentration, high frequency power and substrate temperature etc. that is used to supply with the gas of oxygen atom and/or fluorine atom is effective.
Here, as the material that can become the gas that is used to supply with oxygen atom, can enumerate O
2, CO, CO
2, NO, N
2The gas of O etc., they are gratifying.As the material that can become the gas that is used to supply with fluorine atom, can enumerate fluorine gas (F again,
2), CF
4, SiF
4, Si
2F
6, BrF, ClF, ClF
3Deng gas, they are gratifying.Again,, multiple above-mentioned gas can be mixed, specifically can enumerate CF as can be used in the gas of supplying with oxygen atom and fluorine atom
4And O
2The example of mixed gas, its gratifying example.
The amount of oxygen atom is 1.0 * 10 in the superficial layer 106
17～2.5 * 10
22Atom/cm
3Be gratifying, more preferably 5.0 * 10
17～2.0 * 10
22Atom/cm
3, be preferably 1.0 * 10
18～1.0 * 10
22Atom/cm
3Again, similarly, the amount of fluorine atom is 1.0 * 10 in the superficial layer 106
16～2.0 * 10
22Atom/cm
3Be gratifying, more preferably 5.0 * 10
16～5.0 * 10
22Atom/cm
3, be preferably 1.0 * 10
17～2.5 * 10
21Atom/cm
3
The amount of oxygen atom and fluorine atom can become in the superficial layer 106, for example, and distribution as shown in Figure 3.
Fig. 3 represents an example with the depth section figure of SIMS (secondary ion mass spectrometry with halogen labeling) generation of the peak value of oxygen atom in the instruction card surface layer and/or fluorine atom amount.In Fig. 3, the depth section figure of oxygen atom and/or fluorine atom amount is the situation that has peak value and minimum amount in superficial layer, but the maximum amount in the peak value of oxygen atom, fluorine atom is respectively Omax, Fmax in season, when the minimum amount in the non-single crystalline layers zone of oxygen atom, fluorine atom is respectively Omin, Fmin, wish maximum amount Omax, Fmax, the ratio of minimum amount Omin, Fmin is satisfied the relation of 2≤Omax/Omin≤2000,2≤Fmax/Fmin≤2000 respectively.Best, Omax is 5.0 * 10
20Atom/cm
3～2.5 * 10
22Atom/cm
3, Omin is 2.5 * 10
17Atom/cm
3～1.3 * 10
22Atom/cm
3Scope in.Again, best, Fmax is 5.0 * 10
19Atom/cm
3～2.0 * 10
22Atom/cm
3, Fmin is 2.5 * 10
17Atom/cm
3～1.0 * 10
22Atom/cm
3Scope in.
Here, the minimum amount of definition refers to the region of variation that joins with optical conductive layer not comprising, be stacked on the optical conductive layer with silicon atom and carbon atom minimum value as the amount in the single crystalline layer zone of mother metal.
Again, Fig. 4 is an example of the peak half width in the instruction card surface layer, but the depth section figure of oxygen atom and/or fluorine atom amount is more preferably in the peak value that the amount of oxygen atom in superficial layer, fluorine atom distributes, each peak half width, for oxygen atom more than or equal to 10nm smaller or equal to 200nm, for fluorine atom more than or equal to 10nm smaller or equal to 200nm.
In the present invention, the peak value of the amount of oxygen atom and/or fluorine atom distribution is preferably expressed the shape with certain zone.Specifically, preferably as the peak value at Fig. 3 forms the shape that forms in the zone, express the shape that in the peak value of amount, has the top.When peak value has certain zone, in analysis result, mean that in the thickness direction of superficial layer, oxygen atom and/or fluorine atom exist with certain value.In addition, here our peak value that oxygen atom and/or fluorine atom amount be described forms the zone and is present in situation in the superficial layer 106, even if be that as in the middle layer 108 other the local situation in the non-single crystalline layers zone also is same but for example form location about peak value.
＜top electric charge injects the restraining barrier 〉
In the present invention, for example shown in Figure 1B, the top electric charge that a part that constitutes sensitive layer 102 is set between optical conductive layer 105 and superficial layer 106 injects restraining barrier 107, but with in the situation of Electrophtography photosensor, this is in order to reach the gratifying formation of its purpose effectively at negative charging.
Top of the present invention electric charge injects restraining barrier 107 and stops from top (promptly from superficial layer one side) iunjected charge, can improve charged ability.Again, at least hold 2 greatly regional distributions in order in the zone on optical conductive layer 105 amount of the belonging to group 13 of periodic table element of constituting atom total amount to be had in the thickness direction in the non-single crystalline layers zone, inject the restraining barrier as the top electric charge, for example shown in Fig. 1 D, preferably by middle layer 108 by the 1st top electric charge inject restraining barrier 109 and the 2nd top electric charge inject the restraining barrier 107 such 2 layers constitute.As the amount of above-mentioned belonging to group 13 of periodic table element, have 2 maximum value and/or greatly regional in the thickness direction in the non-single crystalline layers zone at least, the ability of prevention can be further improved, and charged ability can be improved from surperficial iunjected charge.
As above-mentioned belonging to group 13 of periodic table element, specifically, have boron (B), aluminium (Al), gallium (Ga), indium (In), thallium (Tl) etc., the spy is not that boron is most suitable.
Top of the present invention electric charge injects the amount of the belonging to group 13 of periodic table element that contains on restraining barrier 107,109, total amount for constituting atom, in more than or equal to the scope of 60ppm, be preferably in more than or equal in the scope of 100ppm smaller or equal to 3000ppm smaller or equal to 5000ppm.
Top of the present invention electric charge injects the belonging to group 13 of periodic table element that contains on restraining barrier 107,109 both can inject the even distribution that restraining barrier 107,109 enforcements do not depart from the top electric charge, perhaps also can be included in the state of bed thickness direction uneven distribution.But, no matter in which kind of situation, with the surperficial parallel face of matrix in the direction, be not included in the even distribution, from needing for the purpose that reaches the characteristic homogenising the direction in face with departing from yet.
In the present invention, to inject restraining barrier 107,109 and superficial layer 106 identical by silicon atom and the carbon atom non-single crystalline layers as parent is constituted for the top electric charge.Inject silicon atom and the carbon atom that restraining barrier 107,109 is contained at the top electric charge, both can in this layer, implement the even distribution that do not depart from, perhaps also can be included in the state of bed thickness direction uneven distribution.But, no matter in which kind of situation, with the surperficial parallel face of matrix in the direction, be not included in the even distribution, from needing for the purpose that reaches the characteristic homogenising the direction in face with departing from yet.
The amount of the carbon atom that each layer region on electric charge injection restraining barrier 107,109, top in the present invention contains is gratifying to the silicon atom of constituting atom and the summation of carbon atom in more than or equal to the scope of 10 atom % smaller or equal to 70 atom %.Be preferably more than or equal to 15 atom % smaller or equal to 65 atom %.Be more preferably more than or equal to 20 atom % smaller or equal to 60 atom %.
Again, each layer region on top electric charge injection restraining barrier 107,109 preferably contains hydrogen atom in the present invention, and hydrogen atom compensates the not coupling key of silicon atom, improves a layer quality, particularly improves photoconduction electrical characteristics and charge-retention property.The amount of hydrogen atom inject for the top electric charge restraining barrier constituting atom total amount usually more than or equal to 30 atom % smaller or equal to 70 atom %, better more than or equal to 35 atom % smaller or equal to 65 atom %, more preferably greater than equaling 40 atom % smaller or equal to 60 atom %.
In the present invention, electrofax characteristic that the bed thickness separately on electric charge injection restraining barrier 107,109, top is hoped from accessing and economic effect etc., is gratifying more than or equal to 10nm smaller or equal to 1000nm, better more than or equal to 30nm smaller or equal to 800nm, more preferably greater than equaling 50nm smaller or equal to 500nm.When bed thickness during less than 10nm, can not stop fully from a surperficial side iunjected charge, can not obtain sufficient charged ability, cause the electrofax characteristic to descend, when bed thickness surpasses 1000nm, can not expect to improve the electrofax characteristic, but cause the characteristic of sensitivity etc. to descend.
The top electric charge injects restraining barrier 107,109 and preferably changes compositions continuously from optical conductive layer 105 1 lateral surface layers 106, has raising cohesive and the effect that prevents to disturb etc.
Inject restraining barrier 107,109 in order to form top electric charge with the characteristic that can reach the object of the invention, need suitably setting to be used to the mixing ratio of supplying with the gas of silicon atom and being used to supply with the gas of carbon atom, gaseous tension, discharge power and substrate temperature in the reaction vessel.
Again, inject restraining barrier 107,109 at the top electric charge and have situation in the very big zone of the thickness direction of the amount of belonging to group 13 of periodic table element, amount maximum for the belonging to group 13 of periodic table element that improves charged ability characteristics, preferably make the very big zone that is positioned at superficial layer one side.
Equally also design pressure in the choice reaction vessel suitably, it be in the optimum range according to layer, but in common situation more than or equal to 1 * 10
-2Pa is smaller or equal to 1 * 10
3Pa is better more than or equal to 5 * 10
-2Pa is smaller or equal to 5 * 10
2Pa is more preferably greater than equaling 1 * 10
-1Pa is smaller or equal to 1 * 10
2Pa.
Further, suitably select substrate temperature, it is in the optimum range according to layer design, but in common situation, more than or equal to 150 ℃ be challenging smaller or equal to 350 ℃, better more than or equal to 180 ℃ smaller or equal to 330 ℃, more preferably greater than equaling 200 ℃ smaller or equal to 300 ℃.
＜middle layer 〉
In the present invention, for example shown in Fig. 1 C, Fig. 1 D, below the top electric charge injects restraining barrier 107, middle layer 108 is set,, play and improve prima facie concavo-convex bezel ring, effect and improve the fusible effect that the top electric charge injects restraining barrier 107 with in the situation of Electrophtography photosensor at negative charging.Middle layer 108 among the present invention is by silicon atom and the carbon atom amorphous material as parent is constituted.The carbon atom that contains in the middle layer 108 both can have been implemented the even distribution that do not depart from this layer, perhaps also can be included in the state of bed thickness direction uneven distribution.But, no matter in which kind of situation, with the surperficial parallel face of matrix in the direction, be not included in the even distribution, from needing for the purpose that reaches the characteristic homogenising the direction in face with departing from yet.
Again, the amount of the carbon atom that contains in the above-mentioned middle layer 108 is gratifying more than or equal to 40 atom % smaller or equal to 95 atom % to the silicon atom of constituting atom and the summation of carbon atom.Be more preferably more than or equal to 50 atom % smaller or equal to 90 atom %.
In middle layer 108, comprise more carbon atom than above-mentioned electric charge injection restraining barrier 109, the 1st top and electric charge injection restraining barrier 107, the 2nd top again.Further, in middle layer 108, also can contain the belonging to group 13 of periodic table element, but for obtain better effects if of the present invention be make amount for the total amount of the constituting atom in the middle layer smaller or equal to 50ppm.
Be more preferably for 2 very big interregional distances that make adjacency in the thickness direction in the non-single crystalline layers zone of belonging to group 13 of periodic table element amount and smaller or equal to 1000nm the thickness in middle layer 108 controlled more than or equal to 100nm.Again, the thickness in middle layer usually more than or equal to 50nm smaller or equal to 2000nm, better more than or equal to 100nm smaller or equal to 1500nm, more preferably greater than equaling 200nm smaller or equal to 1000nm.
Further in the present invention, in the middle layer shown in Fig. 1 C 108, for example the mode that has a peak value with the amount at dotted line place oxygen atom and/or fluorine atom is controlled.In order to form peak value, when forming the middle layer, wish to flow through the gas that is used to supply with oxygen atom and/or fluorine atom.Again, in order to be controlled at the oxygen atom that contains in the middle layer 108 and/or the amount of fluorine atom, for example, suitably the control accumulating film formation condition of gas concentration, high frequency power and substrate temperature etc. that is used to supply with the gas of oxygen atom and/or fluorine atom is effective.
Here, as the material that can become the gas that is used to supply with oxygen atom, can enumerate O
2, CO, CO
2, NO, N
2The gas of O etc., they are gratifying.As the material that can become the gas that is used to supply with fluorine atom, can enumerate fluorine gas (F again,
2), CF
4, SiF
4, Si
2F
6, BrF, ClF, ClF
3Deng gas, they are challenging.Again,, multiple above-mentioned gas can be mixed, specifically can enumerate CF as can be used in the gas of supplying with oxygen atom and fluorine atom
4And O
2The gratifying example of mixed gas.
The amount of oxygen atom is 1.0 * 10 in the middle layer 108
17～2.5 * 10
22Atom/cm
3Be gratifying, more preferably 5.0 * 10
17～2.0 * 10
22Atom/cm
3, be preferably 1.0 * 10
18～1.0 * 10
22Atom/cm
3Again, similarly, the amount of fluorine atom is 1.0 * 10 in the middle layer 108
16～2.0 * 10
22Atom/cm
3Be gratifying, more preferably 5.0 * 10
16～5.0 * 10
21Atom/cm
3, be preferably 1.0 * 10
17～2.5 * 10
21Atom/cm
3
With the depth section figure that silicon atom and carbon atom are produced as the SIMS of the peak value of the oxygen atom in the non-single crystalline layers zone of mother metal and/or fluorine atom amount that is stacked on the optical conductive layer, in the middle layer, has peak value, oxygen atom in season, maximum amount in the peak value of fluorine atom is respectively Omax, Fmax, oxygen atom, minimum amount in the non-single crystalline layers zone of fluorine atom is respectively Omin, during Fmin, wish maximum amount Omax, Fmax is to minimum amount Omin, the ratio of Fmin satisfies 2≤Omax/Omin≤2000 respectively, the relation of 2≤Fmax/Fmin≤2000.Best, Omax is 5.0 * 10
20Atom/cm
3～2.5 * 10
22Atom/cm
3, Omin is 2.5 * 10
17Atom/cm
3～1.3 * 10
22Atom/cm
3Scope in.Again, best, Fmax is 5.0 * 10
19Atom/cm
3～2.0 * 10
22Atom/cm
3, Fin is 2.5 * 10
17Atom/cm
3～1.0 * 10
22Atom/cm
3Scope in.
Here, the minimum amount of definition refers to the region of variation that joins with optical conductive layer not comprising, be stacked on the optical conductive layer with silicon atom and carbon atom minimum value as the amount in the single crystalline layer zone of mother metal.
＜matrix 〉
As the matrix that uses among the present invention, it is good that electric conductivity is wanted, as conductive base, and, can enumerate the metal of Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, Fe etc. and their alloy, for example stainless steel etc.
Again, even if electrically insulating material, also can be by conductive processing is carried out on the surface that makes a side of light-receiving device with the electrically insulating material of the film of the synthetic resin of polyester, tygon, polycarbonate, cellulose acetate, polypropylene, Polyvinylchloride, polystyrene, polyamide etc. for example or sheet, glass, pottery etc. at least, as matrix.
The base shape of using can be that to have the cylindric or endless of smooth surface or small convex-concave surface banded, suitably determines its thickness in order to form required Electrophtography photosensor.In the situation that requires as the flexible of Electrophtography photosensor, in the scope that can give full play to as the function of matrix, make it thin as much as possible.But, need physical strength etc. from making and handling, make matrix more than or equal to 10 μ m usually.
＜bottom electric charge injects the restraining barrier 〉
In the present invention, shown in Fig. 1 D, it is effective from the electric charge injection restraining barrier 104, bottom of the effect of matrix 101 1 side iunjected charges that prevention has been set on the upper strata of conductive base 101 as Figure 1A.The bottom electric charge injects restraining barrier 104 to have when accepting the charged processing of certain polarity on the Free Surface of sensitive layer 102 at it, stops the function from matrix 101 1 sides to optical conductive layer 105 1 side iunjected charges.
Inject restraining barrier 104 at the bottom electric charge, silicon atom as mother metal, is compared with optical conductive layer 105 described later, contain the impurity that electric conductivity is controlled in more being used to.Inject impurity element that restraining barrier 104 contain with in the situation of Electrophtography photosensor as the bottom electric charge just charged, can enough belonging to group 13 of periodic table elements.Again, with in the situation of Electrophtography photosensor, inject the impurity element that restraining barrier 104 is contained as the bottom electric charge at negative charging, can enough periodic table the 15th family's elements.The amount of the impurity element that the restraining barrier 104 of bottom electric charge injection is in the present invention contained suitably determines according to desirable in order to reach purpose of the present invention effectively, but inject the total amount of the constituting atom on restraining barrier for the bottom electric charge, is gratifying more than or equal to 10 atom ppm smaller or equal to 10000 atom ppm, better more than or equal to 50 atom ppm smaller or equal to 7000 atom ppm, more preferably greater than equaling 100 atom ppm smaller or equal to 5000 atom ppm.
Further, inject restraining barrier 104,, can reach and improve fusible purpose between this electric charge injection restraining barrier 104, bottom and the matrix 101 by containing nitrogen and oxygen at the bottom electric charge.With in the situation of Electrophtography photosensor,, also can have remarkable prevention iunjected charge ability at negative charging by containing nitrogen and oxygen best even if inject restraining barrier 104 impurity element that undopes at the bottom electric charge again.Specifically, the nitrogen-atoms that contains by the holostrome zone of injecting restraining barrier 104 at the bottom electric charge and the amount of oxygen atom, inject the atom total amount of the constituting atom on restraining barrier for the bottom electric charge, make nitrogen and oxygen sum, is gratifying more than or equal to 0.1 atom % smaller or equal to 40 atom %, better more than or equal to 1.2 atom % smaller or equal to 20 atom %, can improve the iunjected charge ability that stops.
Again, be preferably in electric charge injection restraining barrier 104, bottom of the present invention and contain hydrogen atom, at this moment, the not coupling key that hydrogen atom plays existing in the layer compensates, and improves the effect of film quality.The amount that the bottom electric charge injects the hydrogen atom that contains on restraining barrier 104 is gratifying more than or equal to 1 atom % smaller or equal to 50 atom % for the total amount that the bottom electric charge injects the constituting atom on restraining barrier, better more than or equal to 5 atom % smaller or equal to 40 atom %, better more than or equal to 10 atom % smaller or equal to 30 atom %.
In the present invention, electrofax characteristic that the bed thickness on electric charge injection restraining barrier 104, bottom is hoped from reaching and economic effect etc., is gratifying more than or equal to 100nm smaller or equal to 5000nm, better more than or equal to 300nm smaller or equal to 4000nm, more preferably greater than equaling 500nm smaller or equal to 3000nm.By make bed thickness more than or equal to 100nm smaller or equal to 5000nm, can have the ability of sufficient prevention from matrix 101 iunjected charges, can access sufficient charged ability, and can expect to improve the electrofax characteristic, disadvantages such as residual electric potential rising can not take place.
Inject restraining barrier 104 in order to form the bottom electric charge, need suitably set gaseous tension, discharge power and substrate temperature in the reaction vessel.Substrate temperature (Ts) is suitably selected optimum range according to layer design, but in common situation, more than or equal to 150 ℃ be gratifying smaller or equal to 350 ℃, better more than or equal to 180 ℃ smaller or equal to 330 ℃, more preferably greater than equaling 200 ℃ smaller or equal to 300 ℃.Equally also design the optimum range of the pressure in the choice reaction vessel suitably according to layer, but in common situation more than or equal to 1 * 10
-2Pa is smaller or equal to 1 * 10
3Pa is better more than or equal to 5 * 10
-2Pa is smaller or equal to 5 * 10
2Pa is more preferably greater than equaling 1 * 10
-1Pa is smaller or equal to 1 * 10
2Pa.
＜optical conductive layer 〉
Optical conductive layer 105 in the Electrophtography photosensor of the present invention by the non-single-crystal material of silicon atom as mother metal constituted, preferably contains hydrogen atom and/or halogen atom in the layer.This is for the not coupling key to silicon atom compensates, and improves the quality of layer, particularly improves photoconductivity and electric charge retentivity.The amount of the amount of hydrogen atom or halogen atom or hydrogen atom and halogen atom sum is gratifying more than or equal to 10 atom % smaller or equal to 40 atom % for the total amount of the constituting atom in the optical conductive layer, better more than or equal to 15 atom % smaller or equal to 25 atom %.In order to control the hydrogen atom that contains in the optical conductive layer 105 and/or the amount of halogen atom, can control example such as the raw material of the temperature of matrix 101, the hydrogen atom that will be used to contain and/or halogen atom import amount in the reaction vessel, discharge power etc.
Also can in optical conductive layer 105, contain the impurity element of controlling electric conductivity when needing in the present invention.As the impurity element that contains, same with bottom electric charge injection restraining barrier 104, can enough belonging to group 13 of periodic table elements.As the amount of the impurity element that in optical conductive layer 105, contains, for the total amount of the constituting atom in the optical conductive layer more than or equal to 1 * 10
-2Atom ppm is smaller or equal to 1 * 10
4Atom ppm is gratifying, better more than or equal to 5 * 10
-2Atom ppm is smaller or equal to 5 * 10
3Atom ppm is more preferably greater than equaling 1 * 10
-1Atom ppm is smaller or equal to 1 * 10
3Atom ppm.
In the present invention, the bed thickness of optical conductive layer 105 is from accessing the electrofax characteristic of being hoped and economic effect grade according to the suitably decision of being hoped, is gratifying more than or equal to 10 μ m smaller or equal to 50 μ m, better more than or equal to 20 μ m smaller or equal to 45 μ m, more preferably greater than equaling 25 μ m smaller or equal to 40 μ m.
In order to form optical conductive layer 105, need suitably set gaseous tension, discharge power and substrate temperature in the reaction vessel.Substrate temperature (Ts) is suitably selected optimum range according to layer design, but in common situation, more than or equal to 150 ℃ be gratifying smaller or equal to 350 ℃, better more than or equal to 180 ℃ smaller or equal to 330 ℃, more preferably greater than equaling 200 ℃ smaller or equal to 300 ℃.
Equally also design the optimum range of the pressure in the choice reaction vessel suitably according to layer, but in common situation more than or equal to 1 * 10
-2Pa is smaller or equal to 1 * 10
3Pa is better more than or equal to 5 * 10
-2Pa is smaller or equal to 5 * 10
2Pa is more preferably greater than equaling 1 * 10
-1Pa is smaller or equal to 1 * 10
2Pa.
Secondly, we state device and the film formation method that is used to make sensitive layer 102 of the present invention in detail.
Fig. 2 is that expression is used as the pattern pie graph of supply frequency with an example of the manufacturing installation of the Electrophtography photosensor of the high frequency plasma cvd method (also being designated as RF-PCVD briefly) of RF frequency band.Shown in being constructed as follows of manufacturing installation shown in Figure 2.
This device is when roughly distinguishing, by the feedway (2200) of piling apparatus (2100), unstrpped gas, the exhaust apparatus (figure does not draw) that is used for reducing reaction vessel (2111) internal pressure constitutes.In the reaction vessel (2111) in piling apparatus (2100), cylindrical substrate (2112) is set, adds hot basal body, further be connected with high frequency matching box (2115) with well heater (2113), unstrpped gas ingress pipe (2114).
The feedway of unstrpped gas (2200) is by SiH
4, GeH
4, H
2, CH
4, B
2H
6, PH
3Deng the gas cylinder (2221～2226) of unstrpped gas and valve (2231～2236,2241～2246,2251～2256) and mass flow controller (2211～2216) constitute, the gas cylinder of each unstrpped gas is connected by the interior gas introduction tube (2114) of auxiliary valve (2260) and reaction vessel (2111).
Form accumulating film with this device, for example can carry out as follows.
At first, cylindrical substrate (2112) is set in reaction vessel (2111), by unillustrated exhaust apparatus among the figure (for example vacuum pump) to carrying out exhaust in the reaction vessel (2111).Then, by adding on the predetermined temperature that hot basal body is controlled at the temperature of cylindrical substrate (2112) with well heater (2113) 150 ℃ to 350 ℃.
Flow into reaction vessel (2111) in order to be used in the unstrpped gas that forms accumulating film, the valve (2231～2236) of affirmation gas cylinder, the leak valve (2117) of reaction vessel are closed, again, affirmation gas inflow valve (2241～2246), outflow valve (2251～2256), auxiliary valve (2260) are opened, and at first open main valve (2118) to carrying out exhaust in reaction vessel (2111) and the unstrpped gas pipe arrangement (2116).
Secondly, become approximately smaller or equal to the moment of 0.1Pa, close auxiliary valve (2260), gas flows out valve (2251～2256) at the reading of vacuum meter (2119).After this, the valve (2231～2236) of opening the raw material gas cylinder imports each gas from gas cylinder (2221～2226), by pressure regulator (2261～2266) each gaseous tension is adjusted at 0.2MPa.Secondly, open gas slowly and flow into valve (2241～2246), each gas is imported in the mass flow controller (2211～2216).
After finishing the preparation of film forming as described above, form each layer with following order.
At cylindrical substrate (2112) when reaching predetermined temperature, slowly open to flow out and need valve and auxiliary valve (2260) in the valve (2251～2256),, from gas cylinder (2221～2226) predetermined gas is imported in the reaction vessel (2111) by unstrpped gas ingress pipe (2114).Secondly, adjust in order to make each unstrpped gas reach predetermined flow by mass flow controller (2211～2216).At this moment, for being less than, the interior pressure of reaction vessel (2111) equals 1 * 10
2The predetermined pressure of Pa, one side watch vacuum meter (2119) one side to adjust the aperture of main valve (2118).In making, press stable after, the RF power supply (not drawing among the figure) of frequency 13.56MHz is set in required power, by high frequency matching box (2115) RF power is imported in the reaction vessel (2111), produce glow discharge.According to this discharge energy the unstrpped gas that imports in the reaction vessel is decomposed, cylindrical substrate (2112) go up form predetermined with the accumulating film of silicon as major component.After forming required thickness, stop to supply with RF power, close the outflow valve, stop gas and flow into reaction vessel, finish the formation of accumulating film.
By repeatedly repeating same operation, form the sensitive layer of required multi-ply construction.When forming each layer, close the whole outflow valves except the gas of needs, this is self-evident, again, in reaction vessel (2111), from flowing out valve (2251～2256) in the pipe arrangement of reaction vessel (2111), close outflow valve (2251～2256) for fear of each gas residue, open auxiliary valve (2260), further all open main valve (2118), and need correspondingly carry out once will being vented to the operation of high vacuum in the system.
Again, in order to reach film formed homogenising, during cambium layer, by drive unit (not drawing among the figure) at a predetermined velocity slewing circle tubular matrix (2112) also be effective.
Further, can add change in above-mentioned gaseous species and valve operation according to the manufacturing conditions of each layer, this is self-evident.
The heating means of matrix so long as the heater of vacuum mode just can, more particularly, can enumerate the heat radiation lamp heater of the resistance heater, Halogen lamp LED, infrared lamp etc. of the coiling well heater, plate heater, ceramic heater etc. of flake heater, by heater that liquid, gas etc. are constituted as the heat-exchanging part of temperature medium etc.The Facing material of heater block can use metal species, pottery, thermotolerance macromolecule resin of stainless steel, nickel, aluminium, copper etc. etc.
In addition, also can use beyond reaction vessel, the special-purpose container of heating is set, after the heating, in a vacuum matrix is transported to the method in the reaction vessel.
Fig. 5 represents an example with the digital and electronic photographic means of Electrophtography photosensor of the present invention.In Fig. 5, the 500th, the digital and electronic photographic means, the 501st, said Electrophtography photosensor among the present invention, the 502nd, carry out charged corona charging device in order on this photoreceptor 501, to form electrostatic latent image.The 503rd, as the exposure device of electrostatic latent image formation parts.The 504th, be used for supplying with the developer of developers (toner) to the photoreceptor 501 that has formed electrostatic latent image, the 506th, be used for the toner of photosensitive surface is transferred to transfer belt electrical equipment on the transfer materials.The 505th, in order to purify the clearer of photosensitive surface.In order to carry out the even purification of photosensitive surface effectively, carry out the purification of photosensitive surface in this example with elastic drum and cleaning blade.The 507th, in order to prepare the electric light that removes that removes electricity that copying operation next time carries out photosensitive surface.The 508th, fuser.The 510th, the transfer materials of paper etc., the 511st, transport the cylinder of transfer materials.In the light source of exposure L, be the light source of main laser instrument, LED etc. in order to single wavelength.
Use this device, the formation of copy image is for example can followingly to carry out like that.Electrophtography photosensor 501 is rotated to the direction of arrow X at a predetermined velocity, make the surperficial uniform charged of photoreceptor 501 with corona charging device 502.Secondly, on the surface of charged photoreceptor 501, carry out the exposure L of image, on the surface of photoreceptor 501, form the electrostatic latent image of this image.And when the part of the electrostatic latent image on the surface that forms photoreceptor 501 by developer 504 the unit is set the time, supply with toner by developer 504 to the surface of photoreceptor 501, electrostatic latent image is carried out video pictureization (development) become the image that forms by toner, further this toner image is along with the rotation of photoreceptor 501 arrives the unit that is provided with of transfer belt electrical equipment 506, and transfer printing here is by transporting on the transfer materials 510 that cylinder 511 transports.
After transfer printing finishes, remove residual toner with clearer 505 from Electrophtography photosensor 501 in order to prepare next duplicating step, be zero or almost nil further, and remove electricity, finish 1 time and duplicate step with removing electric light 507 in order to make this surperficial current potential.
[embodiment]
Below, be described more specifically the present invention and effect of the present invention by embodiment.Though following embodiment is an example of preferred forms of the present invention, the present invention is not subjected to the qualification of these embodiment.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 1, what the expression summary constituted among making Figure 1A injects the just charged Electrophtography photosensor of using that restraining barrier, optical conductive layer and superficial layer constitute by the bottom electric charge.
In addition, form peak value on the thickness direction of amount in superficial layer for oxygen atom in the superficial layer that makes present embodiment and/or fluorine atom, and in the accumulating film that forms superficial layer, make O
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas changes to Xppm, Yppm, Zppm respectively (all for SiH
4Flow).Specifically, for by in peak value forms the zone, changing each gas flow in certain proportion, have oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value respectively and make.Here, the thickness W that makes peak value form the zone is 100nm.
[table 1]
About the Electrophtography photosensor of such making, with SIMS (CAMECA corporate system, device name: IMS-4F) the depth section figure of the amount of mensuration oxygen atom and/or fluorine atom.As a result, we can confirm that depth section figure as shown in Figure 3 is such, form in the way by the accumulating film at superficial layer and suitably select O
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas can have peak value for the amount of oxygen atom and/or fluorine atom on the thickness direction of superficial layer and makes.
As shown in table 3 in superficial layer forms on the way, by changing O
2Gas, CF
4Gas, CF
4-O
2(30%) mixed gas is for SiH
4Gas flow X, Y, Z[ppm] make Electrophtography photosensor.Evaluation result to each Electrophtography photosensor is as shown in table 3.
Again, about each Electrophtography photosensor, from using SIMS (CAMECA corporate system, device name: the IMS-4F) result of the depth section figure of Ce Dinging, when the minimum amount that is respectively Omax, Fmax, oxygen atom that superficial layer contains and fluorine atom of the maximum amount in the amount distribution peak value of oxygen atom and fluorine atom is respectively Omin, Fmin in season, maximum amount Omax, Fmax are as shown in table 3 to ratio Omax/Omin, the Fmax/Fmin of minimum amount Omin, Fmin.
Comparative example 1
In this comparative example, identical with embodiment 1, on the cylindric aluminum substrate of the diameter 80mm that has implemented mirror finish, under the manufacturing conditions shown in the table 2, what the expression summary constituted among making Figure 1A injects the just charged Electrophtography photosensor of using that restraining barrier, optical conductive layer and superficial layer constitute by the bottom electric charge.
In addition, in this comparative example, in forming surperficial tunic way, do not import O
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas is made, and equally determines that with SIMS the amount of oxygen atom and fluorine atom does not have peak value on the thickness direction in superficial layer.
[table 2]
| Gaseous species and flow | The bottom electric charge injects the restraining barrier | Optical conductive layer | Superficial layer |
| SiH 4[mL/min (normality)] | 150 | 200 | 15 |
| H 2[mL/min (normality)] | 400 | 750 | - |
| B 2H 6[ppm] is (for SiH 4) | 3000 | 0.15 | - |
| NO[%] (for SiH 4) | 5 | - | - |
| CH 4[mL/min (normality) | - | - | 550 |
| Reaction vessel internal pressure [Pa] | 64 | 79 | 60 |
| High frequency power [W] (13.56MHz) | 200 | 600 | 400 |
| Substrate temperature [℃] | 260 | 260 | 260 |
| Thickness [μ m] | 3 | 30 | 0.8 |
In the just charged digital and electronic photographic means iR-6000 that is arranged on CANON (Canon) system of representing among Fig. 5 that summary constitutes with Electrophtography photosensor that makes in embodiment 1 and the comparative example 1, assessment item described later is estimated.Its evaluation result is as shown in table 3.
(1) some repeatability
The Electrophtography photosensor of making is carried in electro-photography apparatus (CANON system, the device of trade name: iR-6000) on, adjust master tape electric current and picture exposure intensity, secondly print the single-point monospace test pattern that each pixel is made laser on-off formation point, ask the mean value of the spot diameter of development.Further, ask the mean value of this spot diameter and the spot diameter of laser (for the 1/e of peak value light quantity Max
2Width, e is the end of natural logarithm) the absolute value of difference, estimate as a repeatability.So this difference is little, the some repeatability is good.
The result who obtains uses the relative evaluation of the value in the comparative example 1 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 1.No problem in the practicality
(2) charged ability
The Electrophtography photosensor of making is arranged in the electro-photography apparatus, on charged device, add+high voltage of 6kV implements corona charging, decides the dark portion surface potential of Electrophtography photosensor with the surface potential instrumentation that is arranged on the developer position.
The result who obtains uses the relative evaluation of the value in the comparative example 1 as 100% o'clock, carries out classification.
AA ... more than or equal to 115%.Very good
A ... more than or equal to 105%, less than 115%.Good
B ... be equal to comparative example 1.No problem in the practicality
(3) sensitivity
Implementing corona charging for Electrophtography photosensor to making, surface potential becomes+450V (dark potential) and after adjusting the current value of charged device, irradiating laser (semiconductor laser of wavelength 655nm) exposes, adjust the light quantity of exposure light source, surface potential is become+50V (bright current potential), with at this moment exposure as sensitivity.
The result who obtains uses the relative evaluation of the value in the comparative example 1 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 1.No problem in the practicality
(4) optical storage
The optical storage current potential is to measure the potential difference (PD) when charged once more behind surface potential in the non-exposure status and the single exposure with same potentiometric sensor under for the appreciation condition of sensitivity.
The result who obtains uses the relative evaluation of the value in the comparative example 1 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 1.No problem in the practicality
[table 3]
| O 2 X[ppm] | CF 4 Y[ppm] | CF 4O 2 Z[ppm] | Omax/ Omin | Fmax/ Fmin | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 1-a | 3 | 0 | 0 | 1.6 | No peak value | A | A | A | A |
| Embodiment 1-b | 4.5 | 0 | 0 | 2.0 | No peak value | AA | AA | AA | AA |
| Embodiment 1-c | 7 | 0 | 0 | 3.4 | No peak value | AA | AA | AA | AA |
| Embodiment 1-d | 25 | 0 | 0 | 12 | No peak value | AA | AA | AA | AA |
| Embodiment 1-e | 1600 | 0 | 0 | 1500 | No peak value | AA | AA | AA | AA |
| Embodiment 1-f | 2300 | 0 | 0 | 2000 | No peak value | AA | AA | AA | AA |
| Embodiment 1-g | 2700 | 0 | 0 | 2500 | No peak value | A | AA | AA | A |
| Embodiment 1-h | 0 | 4.9 | 0 | No peak value | 1.4 | A | A | A | A |
| Embodiment 1-i | 0 | 6.5 | 0 | No peak value | 2.0 | AA | AA | AA | AA |
| Embodiment 1-j | 0 | 8.0 | 0 | No peak value | 2.5 | AA | AA | AA | AA |
| Embodiment 1-k | 0 | 40 | 0 | No peak value | 16 | AA | AA | AA | AA |
| Embodiment 1-l | 0 | 60 | 0 | No peak value | 25 | AA | AA | AA | AA |
| Embodiment 1-m | 0 | 1700 | 0 | No peak value | 1600 | AA | AA | AA | AA |
| Embodiment 1-n | 0 | 2100 | 0 | No peak value | 2000 | AA | AA | AA | AA |
| Embodiment 1-o | 0 | 2350 | 0 | No peak value | 2300 | A | AA | AA | A |
| Embodiment 1-p | 0 | 0 | 8.8 | 1.3 | 1.8 | A | AA | AA | AA |
| Embodiment 1-q | 0 | 0 | 13.5 | 2.0 | 2.5 | AA | AA | AA | AA |
| Embodiment 1-r | 0 | 0 | 30 | 4.5 | 6.1 | AA | AA | AA | AA |
| Embodiment 1-s | 0 | 0 | 65 | 10 | 13 | AA | AA | AA | AA |
| Embodiment 1-t | 0 | 0 | 1800 | 1200 | 1500 | AA | AA | AA | AA |
| Embodiment 1-u | 0 | 0 | 2300 | 1800 | 2000 | AA | AA | AA | AA |
| Embodiment 1-v | 0 | 0 | 2600 | 2200 | 2300 | A | AA | AA | A |
According to the result of table 3, for the amount that makes oxygen atom in the superficial layer and/or fluorine atom has peak value and controls composition in superficial layer, with the comparative example that does not form peak value relatively, can improve a repeatability.Further, about the peak value in the superficial layer, in order to satisfy the relation of 2≤Omax/Omin≤2000 and/or 2≤Fmax/Fmin≤2000, the amount of oxygen atom and/or fluorine atom be distributed in form peak value on the thickness direction embodiment 1-b to 1-f, 1-i to 1-n, 1-q is in 1-u, compare with the comparative example that does not form peak value, can improve a repeatability and charged ability, further increase sensitivity and reduce optical storage, and can reach significant effect simultaneously.
Embodiment 2
Secondly, we discuss the peak half width of oxygen atom and/or fluorine atom.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 1, what the expression summary constituted among making Figure 1A injects the just charged Electrophtography photosensor of using that restraining barrier, optical conductive layer and superficial layer constitute by the bottom electric charge.
In addition, in the present embodiment, about the O that in the accumulating film that forms superficial layer, flows through
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow Xppm, the Yppm of mixed gas, Zppm are (for SiH
4Flow), is controlled at (1) X=6ppm, Y=0ppm, Z=0ppm, (2) X=0ppm, Y=14ppm, Z=0ppm, (3) X=0ppm, Y=0ppm, Z=14.5ppm.Specifically, by in peak value forms the zone, changing each gas flow in certain proportion, form oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value.Again, by only changing the thickness W[nm that each peak value forms the zone] change the peak half width of oxygen atom and/or fluorine atom, make the just charged Electrophtography photosensor of using.
About the Electrophtography photosensor of such making, the result who estimates similarly to Example 1 is illustrated in the table 4.Here peak half width is that the amount of oxygen atom and/or fluorine atom in peak value depth section figure nearby is the spike width (please refer to Fig. 4) at 1/2 place of peak height.
[table 4]
| O 2 [ppm] | CF 4 Y [ppm] | CF 4-O 2 Z [ppm] | W [nm] | Omax/ Omin | Fmax/ Fmin | Oxygen half breadth [nm] | Fluorine half breadth [nm] | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 2-a | 6 | 0 | 0 | 15 | 3.4 | No peak value | 5 | - | AA | A | A | AA |
| Embodiment 2-b | 6 | 0 | 0 | 25 | 3.5 | No peak value | 10 | - | AA | AA | AA | AA |
| Embodiment 2-c | 6 | 0 | 0 | 35 | 3.6 | No peak value | 15 | - | AA | AA | AA | AA |
| Embodiment 2-d | 6 | 0 | 0 | 140 | 3.5 | No peak value | 56 | - | AA | AA | AA | AA |
| Embodiment 2-e | 6 | 0 | 0 | 330 | 3.5 | No peak value | 150 | - | AA | AA | AA | AA |
| Embodiment 2-f | 6 | 0 | 0 | 410 | 3.6 | No peak value | 180 | - | AA | AA | AA | AA |
| Embodiment 2-g | 6 | 0 | 0 | 450 | 3.5 | No peak value | 200 | - | AA | AA | AA | AA |
| Embodiment 2-h | 6 | 0 | 0 | 480 | 3.5 | No peak value | 210 | - | A | AA | AA | A |
| Embodiment 2-i | 0 | 14 | 0 | 15 | No peak value | 4.1 | - | 6 | AA | A | A | AA |
| Embodiment 2-j | 0 | 14 | 0 | 25 | No peak value | 4.2 | - | 10 | AA | AA | AA | AA |
| Embodiment 2-k | 0 | 14 | 0 | 35 | No peak value | 4.3 | - | 14 | AA | AA | AA | AA |
| Embodiment 2-l | 0 | 14 | 0 | 130 | No peak value | 4.2 | - | 50 | AA | AA | AA | AA |
| Embodiment 2-m | 0 | 14 | 0 | 380 | No peak value | 4.1 | - | 170 | AA | AA | AA | AA |
| Embodiment 2-n | 0 | 14 | 0 | 460 | No peak value | 4.2 | - | 200 | AA | AA | AA | AA |
| Embodiment 2-o | 0 | 14 | 0 | 490 | No peak value | 4.2 | - | 220 | A | AA | AA | A |
| Embodiment 2-p | 0 | 0 | 14.5 | 15 | 2.1 | 2.9 | 6 | 8 | AA | A | A | AA |
| Embodiment 2-q | 0 | 0 | 14.5 | 20 | 2.2 | 3.0 | 10 | 12 | AA | AA | AA | AA |
| Embodiment 2-r | 0 | 0 | 14.5 | 30 | 2.3 | 3.1 | 15 | 18 | AA | AA | AA | AA |
| Embodiment 2-s | 0 | 0 | 14.5 | 120 | 2.2 | 3.0 | 50 | 56 | AA | AA | AA | AA |
| Embodiment 2-t | 0 | 0 | 14.5 | 330 | 2.3 | 3.1 | 150 | 180 | AA | AA | AA | AA |
| Embodiment 2-u | 0 | 0 | 14.5 | 400 | 2.2 | 3.1 | 180 | 200 | AA | AA | AA | AA |
| Embodiment 2-w | 0 | 0 | 14.5 | 450 | 2.2 | 3.1 | 205 | 230 | AA | AA | A | A |
| Embodiment 2-x | 0 | 0 | 14.5 | 500 | 2.1 | 3.1 | 215 | 241 | A | AA | AA | A |
Result according to table 4, the embodiment 2-b that forms smaller or equal to 200mm more than or equal to 10mm for the peak half width of the thickness direction of oxygen atom in for superficial layer and/or fluorine atom to 2-g, 2-j to 2-n, 2-q is in 2-u, except can improving a repeatability and charged ability, further can increase sensitivity simultaneously and reduce optical storage.
Embodiment 3
Secondly, we discuss the peak value shape of the amount distribution of oxygen atom and/or fluorine atom.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 1, what the expression summary constituted among making Figure 1A injects the just charged Electrophtography photosensor of using that restraining barrier, optical conductive layer and superficial layer constitute by the bottom electric charge.
In addition, in the present embodiment, about the O that in the accumulating film that forms superficial layer, flows through
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow Xppm, the Yppm of mixed gas, Zppm are (for SiH
4Flow), is controlled at (1) X=5.5ppm, Y=0ppm, Z=0ppm, (2) X=0ppm, Y=12ppm, Z=0ppm, (3) X=0ppm, Y=0ppm, Z=12ppm.Specifically, by in peak value forms the zone, changing each gas flow in certain proportion, form oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value.Again, have in the situation in certain zone, always continue to flow, control in order to make the peak value shape have certain zone with certain flow by in peak value forms the zone, making each gas flow in the peak value shape.
Here, the thickness W of peak value formation regions is 200mm.So similarly make the just charged Electrophtography photosensor of using, the result who estimates similarly to Example 1 is illustrated in the table 5.
[table 5]
| O 2 X[ppm] | CF 4 Y[ppm] | CF 4-O 2 Z[ppm] | Omax/ Omin | Fmax/ Fmin | Oxygen peak value shape | Fluorine peak value shape | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 3-a | 5.5 | 0 | 0 | 3.1 | No peak value | There is not certain zone | - | AA | AA | AA | AA |
| Embodiment 3-b | 5.5 | 0 | 0 | 3.0 | No peak value | Certain zone is arranged | - | A | A | A | A |
| Embodiment 3-i | 0 | 12 | 0 | No peak value | 3.7 | - | There is not certain zone | AA | AA | AA | AA |
| Embodiment 3-j | 0 | 3 | 0 | No peak value | 3.7 | - | Certain zone is arranged | A | A | A | A |
| Embodiment 3-p | 0 | 0 | 12 | 2.0 | 2.6 | - | There is not certain zone | AA | AA | AA | AA |
| Embodiment 5-q | 0 | 0 | 12 | 1.9 | 2.5 | - | Certain zone is arranged | A | A | A | A |
According to the result of table 5, because the peak value that the amount of oxygen atom and/or fluorine atom distributes in the superficial layer does not have certain zone, can improve a repeatability and charged ability, further can increase sensitivity simultaneously significantly and reduce optical storage.
Embodiment 4
Secondly, we discuss the negative charging Electrophtography photosensor in the color electronic camera.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 6, make that the expression summary constitutes among Figure 1B by the bottom electric charge injects restraining barrier, optical conductive layer, the top electric charge that is made of the zone of containing the belonging to group 13 of periodic table element injects the restraining barrier and superficial layer constitutes negative charging Electrophtography photosensor.
In addition, in the present embodiment,, in the accumulating film that forms superficial layer, make O in order to have peak value on the thickness direction of amount in superficial layer that makes oxygen atom in the superficial layer and/or fluorine atom
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas changes to Xppm, Yppm, Zppm respectively (all for SiH
4Flow).Specifically, for by in peak value forms the zone, changing each gas flow in certain proportion, have oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value respectively and make.Here, the thickness W that makes peak value form the zone is 120nm.
[table 6]
Table 8 expression is by gas flow X, Y, the Z[ppm of change list 6] evaluation result of each Electrophtography photosensor of making.
About each Electrophtography photosensor, from using SIMS (CAMECA corporate system, device name: the IMS-4F) result of the depth section figure of Ce Dinging, when the minimum amount that is respectively Omax, Fmax, oxygen atom that superficial layer contains and fluorine atom of the maximum amount in the peak value of oxygen atom and fluorine atom was respectively Omin, Fmin in season, maximum amount Omax, Fmax were as shown in table 8 to ratio Omax/Omin, the Fmax/Fmin of minimum amount Omin, Fmin.
Comparative example 2
In this comparative example, identical with embodiment 4, in the enforcement of diameter 80mm on the cylindric aluminum substrate of mirror finish, under the manufacturing conditions shown in the table 7, make by containing the expression summary constitutes among Figure 1B bottom electric charge and inject restraining barrier, optical conductive layer, inject the negative charging Electrophtography photosensor that restraining barrier and superficial layer constitute by containing top electric charge that layer zone of belonging to group 13 of periodic table element constitute.
In addition, in this comparative example, in forming surperficial tunic way, do not import O
2Gas, CF
4Gas, CF
4-O
2(30%) the gas flow ground of mixed gas makes, and equally determines that with SIMS the amount of oxygen atom and fluorine atom does not have peak value on the thickness direction in superficial layer.
[table 7]
| Gaseous species and flow | The bottom electric charge injects the restraining barrier | Optical conductive layer | The top electric charge injects the restraining barrier | Superficial layer |
| SiH 4[mL/min (normality)] | 120 | 200 | 45 | 18 |
| H 2[mL/min (normality)] | 410 | 800 | - | - |
| B 2H 6[ppm] is (for SiH 4) | - | - | 1000 | - |
| NO[%] (for SiH 4) | 8 | - | - | - |
| CH 4[mL/min (normality) | - | - | 90 | 650 |
| Reaction vessel internal pressure [Pa] | 60 | 75 | 55 | 55 |
| High frequency power [W] (13.56MHz) | 150 | 450 | 150 | 150 |
| Substrate temperature [℃] | 260 | 260 | 260 | 260 |
| Thickness [μ m] | 3 | 30 | 0.2 | 0.4 |
The negative charging made in embodiment 4 and the comparative example 2 to be arranged on the digital and electronic photographic means iR-6000 of the CANON system of transforming in order being used for estimating the negative charging system of representing among Fig. 5 that summary constitutes with Electrophtography photosensor, assessment item described later to be estimated.Its evaluation result is as shown in table 8.
(1) some repeatability
The Electrophtography photosensor of making is carried at electro-photography apparatus (in order to be used to estimate negative charging system reform CANON system, the device of trade name: iR-6000) in, adjust master tape electric current and picture exposure intensity, secondly print the single-point monospace test pattern that each pixel is made laser on-off formation point, ask the mean value of the spot diameter of development.Further, ask the mean value of this spot diameter and the spot diameter of laser (for the 1/e of peak value light quantity Max
2Width, e is the end of natural logarithm) the absolute value of difference, estimate as a repeatability.So this difference is little, the some repeatability is good.
The result who obtains uses the relative evaluation of the value in the comparative example 2 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 2.No problem in the practicality
(2) charged ability
The Electrophtography photosensor of making is arranged on electro-photography apparatus (in order to be used to estimate negative charging system reform CANON system, the device of trade name: iR-6000) in, on charged device, add-high voltage of 6kV implements corona charging, decides the dark portion surface potential of Electrophtography photosensor with the surface potential instrumentation that is arranged on the developer position.
The result who obtains uses the relative evaluation of the value in the comparative example 2 as 100% o'clock, carries out classification.
AA ... more than or equal to 115%.Very good
A ... more than or equal to 105%, less than 115%.Good
B ... be equal to comparative example 2.No problem in the practicality
(3) sensitivity
Implementing corona charging for Electrophtography photosensor to making, surface potential becomes-450V (dark potential) and after adjusting the current value of charged device, irradiating laser (semiconductor laser of wavelength 655nm) exposes, adjust the light quantity of exposure light source, surface potential is become-50V (bright current potential), with at this moment exposure as sensitivity.
The result who obtains uses the relative evaluation of the value in the comparative example 2 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 2.No problem in the practicality
(4) optical storage
The optical storage current potential is to measure the potential difference (PD) when charged once more behind surface potential in the non-exposure status and the single exposure with same potentiometric sensor under for the appreciation condition of sensitivity.
The result who obtains uses the relative evaluation of the value in the comparative example 2 as 100% o'clock, carries out classification.
AA ... less than 85%.Very good
A ... more than or equal to 85%, less than 95%.Good
B ... be equal to comparative example 2.No problem in the practicality
[table 8]
| O 2 X[ppm] | CF 4 Y[ppm] | CF 4-O 2 Z[ppm] | Omax/ Omin | Fmax/ Fmin | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 4-a | 5 | 0 | 0 | 2.5 | No peak value | AA | AA | AA | AA |
| Embodiment 4-b | 0 | 10 | 0 | No peak value | 3.2 | AA | AA | AA | AA |
| Embodiment 4-c | 0 | 0 | 20 | 3.1 | 4.1 | AA | AA | AA | AA |
Result according to table 8, use in the Electrophtography photosensor at negative charging with zone of containing the belonging to group 13 of periodic table element, in order to make the oxygen atom in the superficial layer and/or the amount of fluorine atom in superficial layer, have peak value and control composition, compare with the comparative example 2 that does not form peak value, can improve a repeatability and charged ability, further can improve sensitivity simultaneously and reduce storage.
Embodiment 5
Secondly, we discuss about the negative charging Electrophtography photosensor, the situation that change layer constitutes.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 9, the expression summary constitutes among the construction drawing 1C by the bottom electric charge injects restraining barrier, optical conductive layer, middle layer, the top electric charge that is made of the zone of containing the belonging to group 13 of periodic table element injects the restraining barrier and superficial layer constitutes negative charging Electrophtography photosensor.
In addition, in the present embodiment, have peak value, in the accumulating film that forms the middle layer, make O in order to make the oxygen atom in the middle layer and/or the thickness direction of amount in the middle layer of fluorine atom
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas changes to Xppm, Yppm, Zppm respectively (all for SiH
4Flow).Specifically, for by in peak value forms the zone, changing each gas flow in certain proportion, have oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value respectively and make.Here, the thickness W that makes peak value form the zone is 80nm.
Again.In the present embodiment, silicon atom and carbon atom are injected the restraining barrier as the non-single crystalline layers zone of parent by middle layer, top electric charge and superficial layer constitutes, inject the carbon atom of constituting atom of restraining barrier and superficial layer and the total amount of silicon atom for middle layer, top electric charge, it is identical that the very big zone of carbon atom amount is respectively 70 atom %, as shown in Figure 6, become the distributions that in film thickness direction, have 2 very big zones.And, be formed on the thickness direction of layer region, begin to have the formation of oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value from the minimal value between 2 very big zones of the amount of carbon atom in optical conductive layer one side.
As shown in Figure 6, the zone that the amount that very big zone is a carbon atom is Duoed than the amount of the carbon atom on bottom electric charge injection restraining barrier is also contained in the shape in superficial layer one side in very big zone.About the shape of the amount of presentation surface layer one side, as shown in Figure 9, be illustrated in the shape that the amount of superficial layer one side carbon atom continues to increase and also have very big zone.Again, the shape that distributes at the amount that injects the belonging to group 13 of periodic table element on restraining barrier as Fig. 8 and top shown in Figure 9 electric charge has maximal value.
[table 9]
The negative charging of making among the embodiment 5 is arranged among the digital and electronic photographic means iR-6000 of the CANON system of transforming in order to represent the negative charging system that summary constitutes in the evaluation map 5 with Electrophtography photosensor, carries out the evaluation identical with embodiment 4.This evaluation result of table 10 expression.
[table 10]
| O 2 X[ppm] | CF 4 Y[ppm] | CF 4-O 2 Z[ppm] | Omax/ Omin | Fmax/ Fmin | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 5-a | 5 | 0 | 0 | 2.6 | No peak value | AA | AA | AA | AA |
| Embodiment 5-b | 0 | 10 | 0 | No peak value | 3.2 | AA | AA | AA | AA |
| Embodiment 5-c | 0 | 0 | 20 | 3.2 | 4.1 | AA | AA | AA | AA |
Result according to table 10, use in the Electrophtography photosensor at negative charging with zone of containing the belonging to group 13 of periodic table element, in order to make the oxygen atom in the middle layer and/or the amount of fluorine atom in the middle layer, have peak value and control composition, compare with the comparative example 2 that does not form peak value, can improve a repeatability, further can improve sensitivity simultaneously and reduce optical storage.Again, we judge by in the thickness direction that is formed on layer region, from optical conductive layer one side that the minimal value between 2 very big zones of carbon atom amount begins, formation with oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value can improve sensitivity and reduce optical storage.
Embodiment 6
Secondly, we discuss about the negative charging Electrophtography photosensor, the situation that change layer constitutes.
We are with the manufacturing installation of Electrophtography photosensor with the RF-PCVD method shown in Figure 2, on the cylindric aluminum substrate of the enforcement mirror finish of diameter 80mm, under the manufacturing conditions shown in the table 11, the expression summary constitutes among the construction drawing 1D by the bottom electric charge injects restraining barrier, optical conductive layer, the 2nd top electric charge that is made of the zone of containing the belonging to group 13 of periodic table element injects the restraining barrier and superficial layer constitutes negative charging Electrophtography photosensor.
In addition, in the present embodiment,, in the accumulating film that forms the middle layer, make O in order to have peak value on the thickness direction of amount in the middle layer that makes oxygen atom in the middle layer and/or fluorine atom
2Gas, CF
4Gas, CF
4-O
2(30%) gas flow of mixed gas changes to Xppm, Yppm, Zppm as shown in table 12ly respectively (all for SiH
4Flow).Specifically, for by in peak value forms the zone, changing each gas flow in certain proportion, have oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value respectively and make.Here, the thickness W that makes peak value form the zone is 50nm.
Again.In the present embodiment, with silicon atom and carbon atom as the non-single crystalline layers zone of parent by the 1st top electric charge inject restraining barrier, middle layer, the 2nd top electric charge injects the restraining barrier and superficial layer constitutes, inject restraining barrier, middle layer, the 2nd top electric charge for the 1st top electric charge and inject the carbon atom of constituting atom of restraining barrier and superficial layer and the total amount of silicon atom, it is identical that the very big zone of carbon atom amount is respectively 70 atom %, as shown in Figure 7, become the distributions that in film thickness direction, have 2 very big zones.And, be formed on the thickness direction of layer region, begin to have the formation of oxygen atom peak value, fluorine atom peak value, oxygen atom and fluorine atom peak value from the minimal value between 2 very big zones of the amount of carbon atom in optical conductive layer one side.
Again, in the present embodiment, from using SIMS (CAMECA corporate system, device name: the IMS-4F) result of mensuration depth section figure, (B: boron) amount is for the total amount of constituting atom for the belonging to group 13 of periodic table element on electric charge injection restraining barrier, the 1st top and electric charge injection restraining barrier, the 2nd top, it is identical being 450 atom ppm respectively to the maximum, as shown in Figure 7, become curves with 2 very big zones.
[table 11]
The negative charging of making among the embodiment 6 is arranged among the digital and electronic photographic means iR-6000 of the CANON system of transforming in order to represent the negative charging system that summary constitutes in the evaluation map 5 with Electrophtography photosensor, carries out the evaluation identical with embodiment 5.This evaluation result of table 12 expression.
[table 12]
| O 2 X[ppm] | CF 4 Y[ppm] | CF 4-O 2 Z[ppm] | Omax/ Omin | Fmax/ Fmin | The point repeatability | Charged ability | Sensitivity | Optical storage | |
| Embodiment 6-a | 8 | 0 | 0 | 3.9 | No peak value | AA | AA | AA | AA |
| Embodiment 6-b | 0 | 15 | 0 | No peak value | 4.4 | AA | AA | AA | AA |
| Embodiment 6-c | 0 | 0 | 30 | 4.5 | 6.4 | AA | AA | AA | AA |
Result according to table 12, in order to make the oxygen atom in the middle layer and/or the amount of fluorine atom in the middle layer, have peak value and control composition, compare with the comparative example 2 that does not form peak value, can improve a repeatability, further can improve sensitivity simultaneously and reduce optical storage.Again, we confirm that the 1st top electric charge injects the restraining barrier and charged ability can be improved in electric charge injection restraining barrier, the 2nd top by being provided with.
Claims (7)
1. Electrophtography photosensor, this Electrophtography photosensor have at least on the conductive base by the optical conductive layer that silicon atom is constituted as the non-single-crystal material of mother metal and be stacked on this optical conductive layer with silicon atom and carbon atom as the non-single crystalline layers zone of parent, it is characterized in that:
Above-mentioned non-single crystalline layers zone comprises fluorine atom, thickness direction in this non-single crystalline layers zone, with respect to the constituting atom total amount, the amount of fluorine atom distributes and has peak value, maximum amount in the peak value that the amount of the fluorine atom in the above-mentioned in season non-single crystalline layers zone distributes is the minimum amount of the fluorine atom that contains of Fmax, above-mentioned non-single crystalline layers zone when being Fmin, and the ratio of the minimum relatively amount Fmin of maximum amount Fmax satisfies the relation of 2≤Fmax/Fmin≤2000.
2. Electrophtography photosensor according to claim 1 is characterized in that: have the zone of containing the belonging to group 13 of periodic table element in above-mentioned non-single crystalline layers zone.
3. Electrophtography photosensor according to claim 1 is characterized in that: with respect to the constituting atom total amount in the above-mentioned non-single crystalline layers zone, the thickness direction that the amount of carbon atom is distributed in the non-single crystalline layers zone has 2 greatly zones at least.
4. Electrophtography photosensor according to claim 3, it is characterized in that: the thickness direction in the layer region of more close optical conductive layer one side than the minimal value of carbon atom amount, with respect to above-mentioned constituting atom total amount, the amount of fluorine atom distributes and has peak value, and the minimal value of this carbon atom amount is present between 2 very big zones of above-mentioned carbon atom amount.
5. Electrophtography photosensor according to claim 1 is characterized in that: in the peak value that the amount of the fluorine atom in above-mentioned non-single crystalline layers zone distributes, peak half width is more than or equal to 10nm and smaller or equal to 200nm.
6. Electrophtography photosensor according to claim 1 is characterized in that: the peak value that the amount of above-mentioned fluorine atom distributes does not have certain zone.
7. Electrophtography photosensor according to claim 1 is characterized in that:
Above-mentioned maximum amount Fmax satisfies 5.0 * 10
19Atom/cm
3≤ Fmax≤2.0 * 10
22Atom/cm
3Relation,
Above-mentioned minimum amount Fmin satisfies 2.5 * 10
17Atom/cm
3≤ Fmin≤1.0 * 10
22Atom/cm
3Relation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP284170/2003 | 2003-07-31 | ||
| JP2003284170 | 2003-07-31 | ||
| JP213908/2004 | 2004-07-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410058868.3A Division CN1580960A (en) | 2003-07-31 | 2004-07-30 | Electrophotographic photosensitive member |
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|---|---|
| CN101051192A CN101051192A (en) | 2007-10-10 |
| CN100545757C true CN100545757C (en) | 2009-09-30 |
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| CNB2007101050614A Expired - Fee Related CN100545757C (en) | 2003-07-31 | 2004-07-30 | Electrophtography photosensor |
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| JP5675287B2 (en) * | 2009-11-26 | 2015-02-25 | キヤノン株式会社 | Electrophotographic photosensitive member and electrophotographic apparatus |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659639A (en) * | 1983-09-22 | 1987-04-21 | Minolta Camera Kabushiki Kaisha | Photosensitive member with an amorphous silicon-containing insulating layer |
| CN87101883A (en) * | 1986-02-04 | 1988-04-27 | 佳能株式会社 | The light receiving element that is used for Electronic Photographing Technology |
| CN1167277A (en) * | 1995-08-23 | 1997-12-10 | 佳能株式会社 | Light receiving element |
| CN1264852A (en) * | 1999-01-21 | 2000-08-30 | 佳能株式会社 | Color mixing agent and imaging method |
-
2004
- 2004-07-30 CN CNB2007101050614A patent/CN100545757C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659639A (en) * | 1983-09-22 | 1987-04-21 | Minolta Camera Kabushiki Kaisha | Photosensitive member with an amorphous silicon-containing insulating layer |
| CN87101883A (en) * | 1986-02-04 | 1988-04-27 | 佳能株式会社 | The light receiving element that is used for Electronic Photographing Technology |
| CN1167277A (en) * | 1995-08-23 | 1997-12-10 | 佳能株式会社 | Light receiving element |
| US5738963A (en) * | 1995-08-23 | 1998-04-14 | Canon Kabushiki Kaisha | Light-receiving member for electrophotography having a photoconductive layer composed of a first layer region and a second layer region having different energy bandgaps and characteristic energies |
| CN1264852A (en) * | 1999-01-21 | 2000-08-30 | 佳能株式会社 | Color mixing agent and imaging method |
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| CN101051192A (en) | 2007-10-10 |
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