JPS5895876A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain the photoconductive member characterized by no degradation phenomenon, excellent durability, and absolutely no residual potential, by including carbon atoms in the photoconductive member constituted by an amorphous material wherein silicon atoms are a main body in an uneven, continuous distributed state in the layer thickness direction. CONSTITUTION:The photoconductive member 100 has an amorphous layer 102 having photoconductive property on a supporting body 101 for the photoconductive member. The layer 102 has the main body of the silicon atoms and comprises an amorphous material a-Si (H, X) including hydrogen or halogen atoms. The amorphous layer 102 has a layer constitution comprising a first layer region 103 including the carbon atoms as constituent atoms, a second layer region 104 including atoms (group III atoms) belonging to the group III of the periodic table, and a surface layer region 105 which does not include the group III atoms on the second layer region 104. The carbon atoms included in the first layer region 103 is continuously distributed in the layer thickness direction in said layer region 103, and their distribution state is uneven. It is desirable, however, that the atoms are continuously and substantially evenly distributed in the direction in substantially parallel to the surface of the supporting body 101.

Description

Detailed Description of the Invention The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (herein, light in a broad sense includes ultraviolet light, visible light, infrared light, X-rays, R-rays, etc.). As a photoconductive material for forming a photoconductive layer in a solid-state imaging device or an image forming member for electrophotography in the image forming field or in an original reading device, it has a high sensitivity and a photocurrent (Ip) of 8N ratio [photocurrent (Ip)
/ Has a high dark current (Id), l, has absorption spectral characteristics that match the spectral characteristics of the irradiated electromagnetic waves, has fast photoresponsivity, and has a desired dark resistance value;
No pollution to the human body during use, JI!
For solid-state imaging devices, the ability to easily process afterimages within a predetermined period of time is desirable.Especially for electrophotographic devices that are incorporated into electrophotographic devices used in offices as business machines. In the case of image forming members, the above-mentioned non-pollution during use is an important point.Based on this point, amorphous silicon (hereinafter referred to as A-8I) is a photoconductive material that has been attracting attention recently. For example, German Kubuto No. 2746967, German Publication No. 28
No. 55718 describes its application as an image forming member for electrophotography, and German Publication No. 2933411 describes its application to a photoelectric conversion/reading device. The photoconductive member has electrical properties such as dark resistance, photosensitive armpit, and photoresponsiveness
The reality is that there are still areas where it is necessary to improve the overall properties in terms of optical, photoconductive properties, single-turn properties, and stability over time. For example, when applied to an electrophotographic image forming member, when trying to achieve high light sensitivity and high dark resistance at the same time, it has often been observed in the past that residual potential remains during use. When a photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in a so-called ghost phenomenon, which causes an afterimage.

According to many experiments conducted by the present inventors, a-
Although it has many advantages compared to conventional inorganic photoconductive materials such as Se, OdS, and ZnO, or organic photoconductive materials such as PVOz and TNF%, it has some characteristics that make it unsuitable for use in conventional solar cells. granted fca-8i
Even if the photoconductive layer of an electrophotographic image forming member having a single-layer photoconductive layer is subjected to charging treatment for forming an electrostatic image, the dark decay is extremely fast.
When the photoconductive layer is composed of A-84 material, it is difficult to apply ordinary electrophotographic methods, and it is known that there are aJ points that can be solved. In order to improve electrical and photoconductive properties, hydrogen atoms or halogen atoms in chlorine atoms in fluorine atoms, phosphorus atoms in one elementary atom, etc. to control electrical conductivity, or other properties are added. Therefore, other atoms are contained in the photoconductive layer as constituent atoms, but depending on the abundance of these constituent atoms, the electrical, optical, or photoconductive properties of the formed layer may vary. Problems may occur.

For example, the photocarriers generated in the formed photoconductive layer by light irradiation may not be sufficiently absorbed in the layer, or the injection of charge from the support side may not be sufficiently prevented in the dark area, etc. This often occurs.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, when designing photoconductive members, it is necessary to devise ways to obtain the desired electrical, optical, and photoconductive properties as described above. - The present invention has been made in view of the above points, and aims at the applicability and application of A-8I as a photoconductive member used in solid-state imaging devices, reading devices, etc. in image forming members for electrophotography. As a result of comprehensive research and consideration from the viewpoint of properties, we have developed an amorphous material that uses silicon atoms as its base material and contains at least either hydrogen atoms (I) or Norogen Foshi (X), so-called hydrogenated materials. A photoconductive member having a photoconductive layer composed of amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon (hereinafter RA-8i(H,X)J is used as a generic term for these). The photoconductive member designed and produced with a specific layer structure does not show extremely superior properties in practical use9, but is superior in every respect when compared with conventional photoconductive members;
This is based on the discovery that it has extremely excellent round physical properties especially as a photoconductive member for electrophotography.

The electrical, optical, and photoconductive properties of the present invention are substantially always stable, extremely resistant to light fatigue, and excellent in durability without causing deterioration even after repeated use, and has no or almost no residual potential. The main objective is to provide a photoconductive member that is rarely observed.

Another object of the present invention is that when the present invention is applied as an electrophotographic image forming member, the charge retention ability during charging treatment for electrostatic image formation is sufficient so that ordinary electrophotographic methods can be applied very effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties.

Still another object of the present invention is to provide a photoconductive member for electrophotography that is easy to obtain high-quality images with high density, clear no-fttones, and high resolution. That's true.

Yet another object of the present invention is to provide a photoconductive member having high photosensitivity, high signal-to-noise ratio characteristics, and good electrofishing tactility between the photoconductive member and the support.

[ Composed of Otori-8i (H,X)),
In a photoconductive member having an amorphous layer having photoconductivity, the amorphous layer contains carbon atoms as constituent atoms in a non-uniform and continuous distribution state in the layer thickness direction η-'
1" slow pillow 11'] with a periodicity of 1" and a second layer region containing atoms that exhibit periodicity.

The photoconductive member of the present invention, which is designed to have the above-mentioned layer structure, can overcome all of the above-mentioned problems, and
O exhibits extremely excellent electrical, optical, and photoconductive properties as well as use environment characteristics.Especially when applied as an image forming member for electrophotography, it has excellent charge retention ability during charging processing and is suitable for image formation. It has no influence of residual potential, its electrical characteristics are stable, it is highly sensitive, it has a high signal-to-noise ratio, it has good resistance to light fatigue and repeated use, and it has a high #[), -
The photoconductive member of the present invention will be explained in detail below according to the drawings. The photoconductive member 100 shown in FIG. A photoconductive amorphous layer 102 made of a-8i (H,X) is provided on a support 101 of the present invention. Amorphous layer 1
02 tit, it has a pigeon structure consisting of carbon atoms 104 as constituent atoms and a surface layer region 105 that does not contain any group atoms on the second layer region 104. The carbon atoms contained in the first layer region 103 are continuously distributed in the layer thickness direction in the layer region 103, and the distribution state is non-uniform, but the carbon atoms are substantially distributed on the surface of the support 101. It is preferable that the photoconductive member 100 shown in FIG.
A layer region 105 in which group Ⅰ atoms are not contained in the 0 surface portion.
However, the layer region 105 is provided according to necessity, and is not an essential requirement in the present invention. That is, for example, in Figure 1, the first layer area 103 and the second layer area 104 may be the same layer area, or the second layer area 103 may be in the first layer area 103. The approximately 1 m atoms contained in the second layer region 104, in which the region 104 may be provided, are continuously distributed in the layer thickness direction in the layer region 104, and the distribution state is as follows. It is preferably non-uniform and continuously and substantially uniformly distributed in a direction substantially parallel to the surface of the support 1010.

In the photoconductive member of the present invention, the inclusion of carbon atoms in the 10th layer region provides high dark resistance and improves adhesion between the amorphous layer and the support directly provided. It is measured in In particular, as in the photoconductive member 100 shown in the first panel, a first layer region 103 in which the amorphous layer 102 contains carbon atoms,
It has a 20th layer region 104 containing iris group elements and a surface layer region 105 not containing group 2 atoms, and is shared by the 20th layer region 103 and the 20th layer region 104. Good results are obtained in the case of a layer structure with layer regions).

Further, in the photoconductive member of the present invention, the first layer region 10
The distribution state of the carbon atoms contained in the carbon atoms in the layer thickness direction in the shell layer habitual region 103 Fi1K is the adhesion and contact with the support 101 or other layer on which the class layer region 103 is provided. In order to improve the performance, the distribution performance is made to be higher toward the bonding surface with the support 101 or other layers. Secondly, the carbon atoms contained in the first layer region 103 react with light irradiation from the free surface 11106 @ of the amorphous layer 102.
In order to increase the sensitivity of the surface layer region 105, the free surface 106 is
The distribution fineness is gradually reduced on the side, and the free surface 106
It is preferable that the atoms are contained in the first layer region 103 so that the distribution once becomes substantially zero. Well,
In the case of an example in which the surface layer region 105 of the amorphous layer 102 does not contain the group Ⅰ adenoid, the electrical contact at the bonding surface between the 20th layer region 104 and the surface layer region 105 is In order to smooth the surface layer region 105, the distribution of group (1) atoms in the second layer region 104 is gradually reduced in the direction of the bonding surface with the surface layer region 105, and the distribution of group It is preferable that the distribution state of the Group A atoms is formed such that the concentration is substantially zero. Atoms used as layers in group Ⅰ of the table are B (, [), At (aluminum)
, Ga (gallium), In (indium)
.

Tj (thallium), etc., and particularly preferably used are B and Ga.

In the present invention, the content of Group A atoms contained in the second layer region may be determined as desired so as to effectively achieve the object of the present invention. Usually Fi 1 to 100 based on the amount of silicon atoms constituting
Atomic ppm, preferably 2#50 ato
mic ppm, optimally 3-20 atanic p.
The amount of 1g atoms possessed in the 10th layer region, which is preferably expressed as pm, may be determined as desired depending on the properties required of the photoconductive member in which it is formed. It is determined as appropriate, but in normal cases, 0.01 to 29 atomicq
k is preferably 9.02 to 10 atomic%, preferably 0.03#5 atomic%.

92 to 9 respectively show typical distribution states of carbon atoms and amorphous group atoms contained in the amorphous layer of the photoconductive member in the layer thickness direction in the present invention. In the figure, the horizontal axis indicates the content C of carbon atoms or Figl group atoms, the vertical axis indicates the layer thickness direction of the amorphous layer exhibiting photoconductivity, and the finger indicates the position of the surface on the support side, t8 indicates the position of the surface opposite to the support sacrum. Conclusion 9: The amorphous layer containing carbon atoms and Group A atoms grows from t, 1 lil to ts.

Note that the scale of the horizontal axis is different between carbon atoms and Group 1 Fengzi. Also, in Figures 2 to 9, it is true @A2
~A9, real @B2~B9 tleA distribution concentration line of carbon atoms, distribution all &- of group Ⅰ atoms is shown.

FIG. 2 shows a first typical example of the distribution state of carbon atoms and group atoms contained in the amorphous layer in the layer thickness direction.

In the example shown in 21jAK, an amorphous layer (1,1B) consisting of a-8i(H,X) and exhibiting leading conductivity (1, to t,
The carbon atoms are distributed like this from the support side #f
:04q, and the layer region (111,) (1
, and t, ε), the distribution of carbon atoms gradually decreases in a type 1 manner from 〉1 to substantially zero, and the distribution concentration of the first group Fengzi! is the distribution theory C(2)□
It has a linearly decreasing layer area (also 18) with a housing that decreases from 1 to 18 to substantially zero.

As in the example shown in FIG. 2, an amorphous layer (1, 1B) is provided on the support side. , 4 supports 8. i et al. ,Yo. If there is a layer region (111B) in which the distribution of carbon IA atoms and Group 1 atoms is uniform, the distribution is once 0.
(to) 1 and 0,9□ may be determined as desired depending on the relationship with the support or other layers, but 0
(1) In the case of 1, the normal case is 0.1 for silicon atoms.
~1000 atomic ppm.

It is preferably 1 to 400 atomic ppm, optimally 2 to 200 atomic ppm, and 0
(In the case of @, Siri = +yj [usually 0.0 for children
1-30 atomic chi, preferably 0.02 #20 a
tomiclG, optimally 0.03-10 atoms
It is preferable to use IC9G.

The layer region ("s tl ) tri" is provided mainly to increase photosensitivity, and the layer thickness of the nuclear layer region (1, 1,) is based on the carbon atom distribution concentration CtQ1 and the group The distribution degree is 0 (up to) 1.It is necessary to determine the distribution as desired, especially in relation to the distribution concentration C (goods) 1. In the present invention, the The layer thickness of the layer region (1811) is: A?1100X~
10μ, preferably 200X to 5 tones, and optimally a photoconductive member having a distribution state of particles, while aiming for high light sensitivity and high dark resistance, close contact between the support or other layers. In order to further improve the property of preventing charges from entering the amorphous layer from the support side, it is necessary to attach the amorphous layer to the support @optical surface (1B) as shown by the dashed dot line in Figure 2. (equivalent to the position) in the part,
It is better to provide a layer region (1, 1B) in which the distribution concentration of carbon atoms is less than the distribution concentration 0 (ql).

Layer region where carbon atoms are distributed at high concentration (1211I)
The distribution concentration of carbon atoms in C is usually less than 70 atomic compared to silicon atoms.

Preferably less than 50 atomic$, optimally 30at
It is desirable that the value be omic* or less. The distribution state of carbon atoms in the layer region where carbon atoms and atoms are distributed at a high concentration may be uniform in the layer thickness direction, as shown by the dashed line in Fig. 2, or may be directly bonded. A single chain ff1l is used to improve electrical contact between adjacent layer regions.
As shown in b, the thickness may be set to a constant value of 0 from the support side until a certain thickness, and thereafter gradually decrease continuously until it reaches 0@1.

The distribution state of the group atoms contained in the second layer region in the layer region is such that on the support side, the layer region [layer region (t, tB)] maintains a constant value as the distribution concentration increases. However, in order to more efficiently prevent charge injection from the support side to the amorphous layer, the support side is shown as a dotted chain line C in Figure 2. It is desirable to provide a layer region "(\1.) in which group (I) atoms are distributed with a certain degree of fineness."

In the present invention, it is preferable that the layer region (1, 1,) is provided within 5i from the position 11. Layer region (1, 1,
) may be provided as the entire layer region LT up to 5μ thick, or may be provided as a part of the layer region LT. The layer region (1s1.) may be provided as a part of the layer region L1. The layer area ('s 4m) is determined depending on the electric property required for the amorphous layer to be formed. As for the distribution state in the direction, the maximum Omax of the content distribution value (distribution concentration 11) of the first group atoms is usually more than so atomtc ppm, preferably 8
0 atomic ppm or more, optimally 100 mtan
It is desirable that the layer be formed so as to achieve a distribution state of nic ppm or more.

That is, in the present invention, in the second layer region containing group (III) atoms, the maximum value Gnax of the content distribution exists within 5 μm in layer thickness from the support side (layer region 5 μm thick from 1B). It is preferable that it be formed so as to.

In the present invention, the layer thickness of the layer region (1, 1B) in which carbon atoms are distributed at a high degree and the layer thickness of the layer region (1, 1B) in which group (I) atoms are distributed at a high degree is appropriately determined as desired depending on the content and content distribution state of carbon atoms or Group 1 atoms contained in these layer regions, and is usually 50 A to s pg, preferably 1 iscu tool
It is desirable that the number of people is ~2μ, and the optimal number of Fi2ooX is ~5000 people.The example shown in Figure 3 is basically the same as the nine examples shown in Figure 2, but the difference is that 2
In the case of the example shown in the figure, both the distribution concentration of carbon atoms and the distribution concentration of group atoms begin to decrease at the position t.

In contrast, when it reaches 9 gt, it becomes essentially zero,
In the related case of Figure 3, the distribution of carbon atoms 111 degrees is shifted from the position t, as shown in real [A3, and the distribution of group I atoms is shifted 8 degrees from the position tl, as shown in real 11i183. , respectively begin to decrease, and at the position t, both become substantially zero vC.
, ) is the distribution result [0(2)
The layer area (1,1,) decreases linearly from 1 to substantially zero.

The 20th layer region (1,1,) containing group atoms is:
The layer area (111B) is substantially uniformly distributed at the distribution result [C,, 1, and the distribution line from position t1 is linearly as follows from 0 (to) 1 to substantially zero. It is composed of a layer area (1, 11) that decreases to 11 is a modification of the example shown in FIG. The example shown in FIG. 813 is the same as the case shown in FIG. This is a case where there are two layer regions in which Group 1 atoms are contained in a uniform distribution with a certain distribution concentration.

The amorphous layer in the example shown in FIG. 5 has a layer region containing both carbon atoms and irises group atoms (1, 1B
) and a layer region (1,1,) in which Group 1 Fengzi is contained but no carbon atoms are contained on the layer region (121B).
It is made up of.

Then, the layer region containing carbon atoms (1°tB)
is a layer region (141B) that is distributed substantially uniformly in the layer thickness direction with distribution *10 (1), and a distribution concentration of 0@, which is gradually reduced in the fm manner and reaches substantially zero. It is composed of layer regions (1, 14) that are

Layer region (t, t,) Fi, layer region (tltl) in which the Group A atoms are distributed substantially uniformly from the support side with a distribution #ltLO1x1m, distribution result [04XJ, to distribution concentration C (to).

The layer region (ts
tl) *A layer area with a substantially uniform distribution (1 to 1) with a distribution concentration of 0 (Il) and a layer area with a distribution that continuously decreases linearly from the distribution concentration C (1°) 11) has a laminated layer structure. Figure 6 shows a modification of the example shown in Figure 5. In the case of the example shown in Figure 6, carbon atoms and group A layer region (t4S,) in which carbon atoms are uniformly distributed with a distribution amO,8,O (to), and a layer region (t4S,) in which carbon atoms have a distribution concentration O4c,1
In the layer region (1, 14) in which the number of atoms of the Otori group is gradually decreased linearly to substantially zero, the layer region (1, 1,) and distribution 111 degrees C(2), with substantially uniform distribution state ■
On top of the layer region (1,1,) in which the layer region (1,1,) containing group atoms is provided, there is a layer region (1,1,) in which carbon atoms are not substantially contained. 1,) is provided,
In the layer region (1, 12), the Oto group atoms have a distribution concentration of 0 (ID
It consists of a layer region (1, 12) in which the atoms of the 1st group are uniformly contained, and a layer region (1, 1,) in which the atoms of the 1st group are contained in a state where the distribution is once 0 (to) and gradually decreases. ing.

In FIG. 7, group (I) atoms are contained in the entire region of the amorphous layer [layer region (1, 1,)], and the surface position 1. An example is shown in which group 1 atoms are contained at a distribution concentration of 0 (to).
As shown in the figure, there is a layer region (1, 1B) in which carbon 1A atoms are contained in a uniform distribution state with a distribution concentration of 0°1, and a layer region (1, 1B) in which carbon atoms are contained in a uniform distribution state with a distribution concentration of 11°OQ, and carbon atoms in a distribution state that gradually decreases from 11°OQ to zero. and a layer region (1,1,) containing atoms.

In fact, the distribution of the iris group atoms in the amorphous layer is 0 as shown by @87, that is, the layer region containing the 1st yc atoms (1
,1,) is the layer region (1,1,) in which the Kozen group atoms are uniformly distributed with a distribution of 1111 degrees 0 (to) 1, and the distribution result [
In order to make the distribution change of the Otori group atoms continuous between 0 (to) 1 and the distribution ago, It has a layer region (1, 1,) containing Zokumako.

FIG. 8 shows a modification of the example shown in FIG. 7.

The entire region of the amorphous layer contains carbon atoms and group atoms, as shown by solid lines 8 and 1iB8, respectively, and in the layer region (1, 1,), 1i! , elementary atoms are contained in a uniform distribution state with a distribution concentration of 0 μm, and group 1 atoms are contained in a uniform distribution state with a distribution concentration of 0.1, and the layer regions (1, 11
), the Oto group atoms are contained in a uniform distribution state with a distribution concentration of 0°.

The carbon atoms are in the layer region (1, 1,
), in the 0 layer region (1, 1,) contained in the support layer, the distribution is gradually decreased linearly from Ctdl and becomes substantially zero at position t1. Group atoms are contained in a distribution state that gradually decreases from distribution 1iItL0 (to) 1 to distribution concentration 0°. In the example shown in Figure 9, carbon atoms, Group 1 adenoids are contained in a non-uniform distribution state in the continuously distributed layer ψ region, and the layer region containing carbon atoms (
The layer region (1, 1,) containing group II adenoids
11B) is provided.

In the layer region (1, 1,), carbon atoms have a distribution concentration go, 1, and the distribution concentration of the first Tic atom is 0 (to) 1.
2, each of which is substantially uniformly contained with a certain distributed acidity.
9. In the layer region (1, 1,), carbon atoms and No. 1 group Fengzi are contained in such a way that their distribution gradually decreases as the layer grows, and in the case of No. In this case, the distribution of wrinkles is virtually uniform.

Carbon atoms are present in the layer region (1,
11) is contained so as to form a linearly decreasing distribution state, and the distribution shape IIA is substantially zero at t8.6 As shown above, from FIGS. We will explain some typical examples of the distribution state of carbon atoms and group atoms contained in the material layer in the layer thickness direction. Support as described -
1g of charcoal or a portion with a high content of 111 degrees C of Group 1 atoms is formed on the surface t side, where a distribution state is formed where the content concentration 0 is considerably lower than on the support side. Nine layer areas may also be provided.

In the present invention, specific examples of the halogen atom (X) contained in the amorphous layer if necessary include fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. It can be mentioned as.

In the present invention, the amorphous layer composed of a-8i (H, Ru. For example, to form an amorphous layer composed of a-8i()l,X) by the glow discharge method, basically silicon atoms (8i)
Along with the raw material gas for 8i supply that can supply hydrogen atoms (
H) A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge within the deposition chamber, and is pre-installed at a predetermined position. It is sufficient to form a layer consisting of a-81 (H, 8 in a zero atmosphere of a mixed gas of 9.
When sputtering a target composed of i, it is preferable to introduce a gas for introducing water bulk atoms (H) or Fi/halogen atoms (X) into the deposition chamber for sputtering.

The raw material gas for S1 supply used in the present invention includes 8iH,,8i1H,,8i,H,,Si'4H,
Silicon hydride (silanes) in a gaseous state such as No. 6 or which can be gasified can be effectively used. In particular, Si
Preferred examples include H4,8i1H.

Many halogen compounds are effective as the raw material gas for introducing halogen atoms used in the present invention, such as halogen gas, halides, interhalogen compounds, halogen-substituted silane derivatives, etc. Preferable examples include halogen compounds that can be gasified. In addition, silicon compounds that are in a gaseous state or that contain halogen atoms and can be gasified are also effective in the present invention. Examples of halogen compounds that can be suitably used in the present invention include fluorine, chlorine, bromine, and iodine gas, BrF, OIF,
OIF,.

BrFl, BrF, , IP, , IF, ,
Mention may be made of compounds between /11 C177 of IOj, IBr%.

Specifically, examples of silicon compounds containing halogen atoms, silane derivatives substituted with halogen atoms, etc.
%F4 * it t F@ , 8 k Oj4 *
Preferred examples include silicon halides such as 81Br4.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using such a silicon compound containing a halogen atom, silicon hydride gas as a raw material gas capable of supplying 8i is not used. Both are a-si on a predetermined support.
:can form an amorphous electrolytic layer consisting of Gas and Ar.

Gases such as Hl, He, etc. are introduced into a deposition chamber in which an amorphous layer is formed at a predetermined mixing ratio and gas flow rate, and a glow discharge is generated to form a plasma atmosphere of these gases. However, in order to introduce hydrogen atoms, a silicon compound gas containing water atoms is also mixed with these gases under a specified lid. A layer may also be formed.

Moreover, each gas may be used not only as a single species but also in a plurality of tanks mixed at a predetermined mixing ratio.

To form an amorphous layer consisting of a-8i (H, This is sputtered in a predetermined gas plasma atmosphere, and in the case of the ion blating method, it is heated and evaporated by a resistance heating method, or an electron and beam method (BB method), etc., and the flying evaporates are sputtered in a predetermined gas plasma. 1 #1 A fist can be made by passing air through it.

In order to introduce halogen atoms into the layer formed by either the sputtering method or the ion blasting method, the halogen compound or the bulky compound containing the halogen particles is added to the deposition chamber. It is sufficient to introduce the gas and form a plasma atmosphere of the gas.Also,
In the case of introducing hydrogen atoms, a raw material gas for introducing water bulk atoms, such as Hl or a gas such as the nine silanes mentioned above, is introduced during layer deposition for sputtering to form a plasma atmosphere of the gas. Good @ In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the raw material gas for introducing -halogen atoms.
In addition, m”, Hot.

Hydrogen hegenide such as HBr, Hl, 8iH1F1
, SiH,I.

8! H, Otl, 81kiD! , , 8iH,B
halogen-substituted water voluminized silicon such as rl, 8iHBr, etc.
Gaseous or gasifiable halides containing water atoms as one of the -12 elements can also be cited as effective starting materials for forming an amorphous layer. Chloride is suitable for halogen introduction in the present invention because when forming an amorphous layer, halogen atoms are introduced into the layer and water atoms, which are extremely effective for controlling electrical or photoelectric properties, are also introduced. used as raw material.

In order to structurally introduce hydrogen atoms into the amorphous layer, in addition to the above, H3, 8iH4, 8i1H, 84,H, etc.

This method can also be achieved by causing a discharge by causing a 5i4H silicon hydride gas to coexist with a silicon compound for supplying Si in the deposition chamber. For example, in the case of the reactive sputtering method, an 8i target can be A gas for introducing halogen atoms, H, and gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma atmosphere, and the St metal is sputtered. By doing this, a-
An amorphous layer consisting of 8i'(H,X) is formed.

Furthermore, a gas such as BtHs can also be introduced for doping with impurities.

In the present invention, the amount of hydrogen atoms (H) or halogen atoms (X) contained in the amorphous layer of the photoconductive member to be formed
The sum of the amounts of violet or water bulk atoms and halogen atoms is usually 1 to 40 atomiclg, preferably 5 to 30 at
omicIs is desirable. To control the violet of water bulk atoms (H) and/or halogen atoms (X) contained in the amorphous layer, for example, the support temperature or Fi/ and water
The amount of the starting material used to contain the A atom (i()) or the halogen atom (X) introduced into the deposition apparatus system and the force of the discharge may be controlled.

In the present invention, the diluting gas used when forming the amorphous layer by the glow discharge method or sputtering method is as follows:
Rare gases such as He and Ne.

Ar and the like can be cited as suitable materials. ・For forming the first layer region and the second layer region by introducing carbon atoms and atoms of the group P of the periodic table into the amorphous layer. , by using glow discharge method, reactive sputtering, or both starting materials together with the above-mentioned starting materials for forming an amorphous layer, and controlling and incorporating OJi into the formed layer. When the glow discharge method is used to form the first layer region constituting the crystalline layer, the starting materials serving as the raw material gas for forming the tenth layer region include the above-mentioned nine amorphous layer forming materials. A starting material for introducing a carbon atom is added to 4, which is selected as desired from among the starting materials. As such a starting material for introducing carbon atoms, most of the gaseous substances containing at least carbon atoms or gasified substances that can turn into cancer can be used.

For example, a raw material gas whose constituent atoms are silicon atoms (8i) and a raw material gas whose constituent atoms are carbon atoms (0) are
Hydrogen atom (H) or and halogen atom <X depending on 1'
> are mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si) and carbon atoms (0) and hydrogen atoms (H) are used.
A raw material gas containing constituent atoms is mixed at a desired mixing ratio, or a raw material gas containing silicon atoms (Si), carbon atoms (0), and It can be used in combination with a raw material gas whose constituent atoms are three hydrogen atoms (H) ◎Also, a raw material gas whose constituent atoms are silicon atoms (8i) and hydrogen atoms (11) can be used. A raw material gas having carbon atoms (0) as a constituent atom may be mixed and used.

Starting materials that can be effectively used as raw material gases for introducing carbon atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene/carbon atoms having 2 to 5 carbon atoms, and saturated hydrocarbons having 0 and H as constituent atoms. and acetylene hydrocarbons having 2 to 4 carbon atoms.

In terms of variants, saturated hydrocarbons include methane (OH4),
-C tough (OtHs), propane (CmHa),
n-butane (n-04H,.), bebutane (0,H
□), 'Ethylene hydrocarbons include ethylene (OJ
L ) + propylene (0,H,), butene-1
(OtHa), buty/-2(OaHa)-isobutylene (04Ha)-pentene (0*H1a).

Examples of acetylene hydrocarbons include acetylene (0tHt
) = methylacetylene (0,H,), butyne (o
, it, ) and the like.

As a raw material gas containing Si, C, and H as constituent atoms, S
Examples include alkyl silicides such as i (OHn)a -Sj (0xHs)a.

To form the first layer region containing carbon atoms by the sputtering method, a single crystal or polycrystalline 8i wafer or C wafer, or a wafer containing a mixture of 8i and C is used as a target. , these may be performed by sputtering in various gas atmospheres.

For example, when used as a %aiSi wafer target, the raw material gas for introducing carbon atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary, and the material gas is used in a deposition chamber for sputtering. The Si wafer may be sputtered by introducing these gases into the Si wafer and forming a gas plasma of these gases.

Alternatively, by using Si and C as separate targets, or by using a single target containing 8i and 00, the dilution gas atmosphere as a sputtering gas can be improved.
Sputtering is performed in air or in a gas atmosphere containing at least hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms. As the raw material gas for carbon atom introduction, the raw material gas for carbon atom introduction among the raw material gases shown in the glow discharge example described above can be used as an effective gas also in the case of sputtering.

In the present invention, the genus 10 constituting the amorphous layer contains carbon atoms in a skin-like manner as described above.
Furthermore, at least one of an oxygen atom or a nitrogen atom may be contained for the same purpose as a carbon atom and according to the same method of containing 1g of charcoal.

Oxygen atoms can be used as starting materials that can be used as raw material gas for introducing nitrogen atoms.
For example, oxygen (pseudo), ozone (Os), -carbon oxide (
00), carbon dioxide (Cot), -nitrogen oxide (NO)
, nitrogen dioxide (NO,), -nitrogen dioxide (NyoO), nitrogen sesquioxide (Nm9m) -nitrogen tetroxide (N*Oa),
Nitrogen sesquioxide (N, 0.), nitrogen trioxide (NO,).

1 whose constituent atoms are 8i, O, and H, for example, disiloxy?
:/H1Si08iH3,) ') V a *?
yH, 8; 08iH, 08iH.

lower siloxanes such as nitrogen (
Nf), or nitrogen compounds such as gaseous or gasifiable nitrogen, nitrides, and azides containing N and H as constituent atoms; 〇When forming the layer region by sputtering method, use of Sin, Si, N.

or a mixture of these as a target, or 8i and Sin, or 8i,
N, a mixture of nine, or 8i and 8i0. and 8i,
N.

Oxygen atoms in the second layer region by using a mixture of and as a target.

At least one of nitrogen atoms can be contained.

Mysteriously, the targets are 0 and 8i0. , or 8i,
A mixture of N, or 0 and SiO83
. It is a good idea to introduce a gaseous or gasifiable starting material for introducing Group A atoms into a vacuum deposition chamber for forming an amorphous layer together with a raw material gas for forming a crystalline layer. It is.

The content of group A atoms introduced into the second layer region is determined by controlling the gas flow rate, gas flow rate ratio, discharge power, etc. of the starting material for introducing group group atoms introduced into the deposition chamber. In the present invention, the starting materials that can be controlled arbitrarily for introducing boron group atoms include B, H,
6,B,H,,,BP, ,B,H,,,B6H,.

. B@Hst -BJ (Boron hydride such as +4, BP,
BO/,, BBr.

Examples include boron halides such as. In addition, A10/
s, Gap? ,, Ga(OH,)1 , Ink/
, , Tl0I, etc.4 can be mentioned.

In the present invention, a transition layer region (a layer region in which the distribution concentration of either carbon atoms or group atoms changes in the layer thickness direction)
The formation of is achieved by suitably varying the flow rate of the gas containing the component whose distribution concentration is to be varied. For example, it is preferable to gradually change the opening of a predetermined needle valve provided in the middle of the gas flow path system by using any commonly used method such as manual operation or an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve.

When creating an amorphous layer, even if the plasma state is maintained or interrupted at the boundary between the transition layer region and other layer regions, it will not affect the properties of the film, but it is best to perform it continuously. Also preferred from the viewpoint of management: The thickness of the amorphous layer is determined as desired so that the photocarriers generated in the non-laminar layer are transported efficiently, and is usually 3% to 100%. /J*
It is preferably 5 to 504%.

The support used in the present invention may be electrically conductive or electrically insulating. Examples of the conductive support include Ni0r and stainless steel.

Aj, Or, Mo, Au, Nb, Ta, V, Ti,
Metals such as Pt and Pd or alloys thereof may be mentioned○
``Electrically insulating supports include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, and polyvinyl chloride.

Films or sheets of synthetic resins such as polychloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the surface that has undergone conductive relief.

For example, if it is glass, Ni0r is applied to its surface.

Aj, Or, Mo, Au, Ir, Nb, Ta, V, T
i, Pt, Pd.

In, 03, SnO, ITO (In, 0.+8
Conductivity is imparted by providing a thin film consisting of nO, ), etc., or if it is a synthetic resin film such as a polyester film, Ni0r, Aj, Ag, Pb, Z
n, Ni, Au.

A thin film of metal such as Or, Mo, Ir, Nb, Ta, V, Ti, Pi, etc. Conductivity is imparted to the surface by providing it on its surface by vapor deposition, electron beam evaporation, sputtering, taring, etc., or by laminating the surface lm with the above-mentioned metal. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If used as a material, F is recommended for continuous high-speed copying.
i. It is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support #-j% is determined as appropriate so that the desired photoconductive member can be formed, but if flexibility is required as a photoconductive member, it is necessary to have sufficient lateral performance as a support. If the effect is within the range, it will be made as thin as possible. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., in the photoconductive member of the present invention, the thickness is usually 10μ or more. It is preferable to provide a surface layer called a so-called barrier layer which has the function of blocking charge injection into the amorphous layer from the free surface side. The upper layer provided on the amorphous layer has silicon atoms as its base material, and contains at least one type of atom selected from carbon atoms (C) and nitrogen atoms (N), and hydrogen atoms or hydrogen atoms as necessary. Amorphous materials containing at least one of halogen atoms (these are collectively referred to as a (8t 1(C
e N), -x ) (He X)ry (
however.

0<1.0<y<1)>, or an electrically insulating metal oxide or an electrically insulating organic compound.

In the present invention, F, C, By, 1 are preferable as the atom (X) contained in the upper part 1, and F and Cd are particularly preferable. Specifically, examples of materials that can be effectively used as amorphous materials include:

As a carbon-based amorphous material, a-8 import C)-1゜'-(
SlbCrb)CHl−Ce” (81dC+−
d) eXte.

a (81fC, -f)g(H+X)+ -g e
As a nitrogen-based amorphous material a 81hHi-h e a
(8jiNt-i)jHt-j ea-(81hN1
-h) JXr4, a-(81mNI-ffI)
n(H+X), -! Furthermore, among the above amorphous materials, examples include amorphous materials containing two types of atoms, C and N, as constituent atoms (however, so<”ebp
' e ' * ” 9 ' I ' I btm *
j * k−j−□,. 1).

These amorphous materials can be appropriately forged depending on the characteristics required for the surface layer through the optimized design of the layer structure and the elegance of continuous production of the amorphous layer provided in contact with the surface layer. From the viewpoint of characteristics, it is more preferable to select a carbon-based amorphous material.

When the surface m' is made of the above-mentioned amorphous material, the layer formation method may be a glow discharge method, a sputtering method, an ion implantation method, an ion blating method, an electron beam method, or the like.

When the surface layer is composed of the above-mentioned amorphous material, it is carefully formed so that the required properties are imparted as desired.

In other words, a substance whose constituent atoms are 8i, at least one of C, N, and optionally H or/and In terms of physical properties, it shows properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties. In the optical region, an amorphous material is formed that is non-photoconductive and has high dark resistance.
The conditions for its creation are strictly selected.

carbon atoms, nitrogen atoms and hydrogen atoms contained in the surface layer,
The amount of halogen atoms, as well as the conditions for forming the surface layer, is an important factor in forming an upper layer with desired properties.

When the surface layer is composed of a-8j @C1-a, the content of Fi carbon atoms is usually 60 to 60 to silicon atoms.
90 mtomlc %, preferably V165-80 a
tomic%.

For moths, 70-75 atomic %, #i0.1-0,4. Preferably 0.2 to 0.35.
The optimal value is 0.25 to 0.3, and a-(5HbC
, -b,) cHz-c, the carbon atom content is usually 30 to 90 atomic %, preferably K rj 40 to 90 atomic %, maximum J K
1j50-80 atomic%, hydrogen atom content is usually 1-40 atomic%, preferably 2-35 atomic%, optimally 5-30 atomic%.
If shown in atomic %, b, c,
b is usually 0.1 to 0.5. Preferably 0.1 to 0.35
, optimally 0.15-0.3, C-# typically 0.
60 to 0.99, preferably 0.65 to G,95, optimally 0.7 to 0.95, and a-(8id01-
d) eXl-e or a-(5ifOt-f)
When composed of g (H+X)t-g, the content of longitudinal atoms is usually 40 to 90 atomic −.

The amount of dead metal is preferably 50 to 90 atomic %, preferably 60 to 80 atomic % for eel, and the amount of dead metal in the combination of halogen atoms or halogen atoms and hydrogen atoms is usually 1 to 80 atomic %.
20 atonic%, preferably 1-18 atonic
mic%, optimally 2-l5 atomic%
When both halogen atoms and hydrogen atoms are contained, the hydrogen atom content is usually 19 atomic'l
t'L or less, preferably 13 atomic% or less
@ d p e-p f p g Q Display text is d
, f is usually 0.1 to 0.47. Suitably 0.1 to 0.
35. Optimal is 0.15-0.3, e, g is normal line 0.8-0.99. The angle is preferably 0.85 to 0.99°, and most preferably 0.85 to 0.98.

When the surface layer is composed of a nitrogen-based amorphous material, it is usually 43-60 atomic % based on silicon atoms.

Suitably 43-50 atomic9G, h is usually 0.43-O, SO, suitably 0.43-0
．． It is said to be 50.

When composed of a (SiiNl-i)jHt-j, the 1 element content is normally 25 to 55 a
tomic-.

Suitably 35-55 at(2)tc*e Hydrogen atom content is usually 2-35 atomic%
, preferably 5 to 3 Q atomics, 'e
If expressed as J, 11 is usually 0.43 to 0.6. Preferably 0.43' to 0.5. j is usually 0.65~
0.98. It is preferably set to 0.7 to 0.95, and a −(
8ikNx-kMXl-j or a-(51mN1-m
)n(Hx)1-n, the content of nitrogen atoms is usually 30 to 6 Q atomic,
The content of halogen atoms or the combined content of halogen atoms and hydrogen atoms is preferably 1 to 20 atomic%, preferably 2 to 15 atomic%.
omic-, and when both a halogen atom and a hydrogen atom are contained, the hydrogen atom content is usually l 9 at
omic% or less, preferably 13 atomic$ or less, and Id in terms of k, j, m, and n,
1 is usually 0.43 to 0.60. Preferably 0.43 to 0
．． 49°III, fl is usually 0.8 to 0.99.
Preferred examples include electrically insulating metal oxides constituting the surface layer and MgO, which are preferably 0.85 to 0.98.
The surface layer may be formed by using more than one species in combination.

The formation of a surface layer composed of electrically insulating metal oxides is
Vacuum evaporation method, CVD
The thickness of the surface layer is formed by the rd@pos method, glow discharge scaling method, sputter ring method, ion implantation method, iodine plating method, electron beam method, etc. Numerical range 1L One of the important factors to effectively achieve the purpose is that if the thickness of the surface layer is sufficiently thin, the charge in the amorphous layer from the surface side of the surface layer In addition, if there are more than enough species, the probability of coupling of photocarriers generated in the amorphous layer by light irradiation with charges on the surface layer becomes extremely high. becomes smaller and thus the purpose of providing one surface II cannot be effectively achieved in any case.

In view of the above points, the thickness of the surface layer in order to effectively achieve the purpose of providing the surface layer is usually 305 to 50 mm.
μ, preferably 505 to 1 μ.

Next, a method for manufacturing a photoconductive member produced by a glow discharge decomposition method will be described.

FIG. 10 shows an apparatus for manufacturing photoconductive members using the glow discharge decomposition method.

Gas cylinders 1002, 1003, and 1004 in the figure contain diluted 8iH gas (purity 99.999 *
, hereinafter abbreviated as 8t H4/He0) Cylinder, 10
03 diluted with He n9B, H, gas (pure ['99.9
99%, hereinafter abbreviated as Bxis/Ha. ) cylinder, 1004.1005 is CH, gas (pure [99,
99%) diluted with 1006 ij He
8+F, gas (purity 99.999%, hereinafter 8iF)
, /Ha is abbreviated. ) It is a cylinder.

In order to flow these gases into the reaction chamber 1001, pulps 1022 to 1026 of gas cylinders 1002 to 1006 are used.
, the leak pulps 1035 are respectively closed, and also check the inflow pulps 1012 to 1016, the outflow pulps 1017 to 1021, and the auxiliary pulps 1032 and 103.
Make sure that 3 is open and first press main pulp 10.
34? It is opened to exhaust the reaction chamber 1001 and the gas piping.

At this point, the auxiliary valves 1032, 1033, for example when pulp flows out, the gas cylinder 1002
iH number/)k gas, BtHs/ from gas cylinder 1003
Pulp 1022 , 1023 , 1025 is opened, outlet pressure gauge is used, and mass flow controllers 1007 , 10 are supplied with He gas and CH gas from gas cylinder 1005 .
Gases 08 and 1010 are introduced into the reaction chamber 1001. At this time, 8 i HjHe gas flow rate and B, H・
/H4! Outflow pulp 1017, 1018, 1 so that the ratio of gas flow rate to CH4 gas flow rate becomes a desired value.
020 and also confirmed that the vacuum gauge 1036 is set at a temperature of 50 to 400°C by the heater 1038 so that the pressure inside the reaction chamber reaches the desired value. The pulps 1018 and 10 are controlled manually or by an external drive motor, etc., by setting the electric power to
The concentration of Group 1 atoms such as B and carbon atoms contained in the formed layer is controlled by gradually changing the concentration for 20 days.

Needless to say, when forming each layer, the gas used to form the previous layer flows into the reaction chamber 1001 and the outflow pulp 1017. 1021 to the inside of the reaction chamber 1001, the outflow valves 1017' to 1021 are closed, and the auxiliary valve 1032 is closed.
, 1033, fully open the main pulp 1034, and temporarily evacuate the system to a high vacuum, if necessary.

An example below will be described in which the base cylinder 1037 is rotated at a constant speed by a motor 1039K in order to make the thickness of the layer uniform while forming a single layer.

Practical example 1 Boron (B) and carbon (
Using the content of C) in the layer as a parameter, an amorphous layer having the configuration shown in FIG. 2 was formed on the AI cylinder to produce a one-image forming member for four electron beams. The common manufacturing conditions at this time are the content C(α) of the primary element, and the evaluation results of the obtained samples are shown.

The fabricated electrophotographic image forming member undergoes a series of electrophotographic processes from charging, exposure, development, and transfer to achieve the desired density, decomposition power, and gradation that are visualized on the transfer paper. Reproducibility], etc., were evaluated on a four-point scale.

Table 1 Example 2 Using the manufacturing apparatus shown in FIG. 10 and using the contents of borium* (B) and carbon (0) in the layer as parameters, a non-woven fabric having the layer structure shown in FIG. 3 was prepared on the Aj cylinder. A crystalline layer was formed to obtain an electrophotographic imaging member. The preparation conditions for each layer region constituting the amorphous layer at this time are shown in Table 3 below.

Using the obtained electrophotographic image forming member, a toner image was repeatedly formed on a transfer paper by applying the Oniko Photo process in the same manner as in Example 1.

A stable, high-quality toner transfer image could be obtained.

311 Discharge layer II-: IL5aMHz Example 3 Using the manufacturing apparatus shown in FIG.
Using the content of (0) in the layer as a parameter, an amorphous layer having the layer structure shown in FIG. 4 was formed on the cylinder to obtain an electrophotographic image forming member. The conditions for creating each layer region constituting the quality layer are shown in Table 4 below. Using the obtained electrophotographic image forming member, a toner image was formed on a transfer paper by applying the electrophotographic process in the same manner as in Example 1. By repeatedly forming ζ, a stable high-quality toner transfer image could be obtained. , 硼* (B)
and the content of carbon (0) in the layer as a parameter,
An amorphous layer having the layer structure shown in FIG. 5 was formed on the kl cylinder to obtain an electrophotographic image forming member. Example 1 using each of the electrophotographic imaging members shown in Table 5.
When donor images were repeatedly formed on transfer paper using the same electrophotographic process, the evaluations shown in Table 6 could be obtained.

However, X(4) in Table 5 is as follows.

54-1...lXl0-' 84-2...
...5 X i O-'54-3...1×I
O″″'84-4...5X10-'llll
5 Surface discharge frequency 11 MHz: 6-MHz Toron Example 5 Using the manufacturing equipment shown in Figure 10, using the content of boron (B) and carbon (0) in the layer as parameters, An electrophotographic image forming member was obtained by forming an amorphous layer having the layer structure shown in FIG. 6. The conditions for forming each layer region constituting the amorphous layer are shown in Table 7 below. Show friend.

Using each of the obtained electrophotographic image forming members, toner images were repeatedly formed on transfer paper using the same electrophotographic process as in Example 1, and the evaluations shown in Table 6 were obtained. done.

However, X(5) in Table 7 is the following 085-1
・・・・・・1×lO″″’85-2・・・・・・5×
10″″7S5-3・・・1×10″″’85-
4...Song 5X10'''''85-5-----IXIO
-'85-6---2X10-''5s-r-;
-----1x1o-" 85-8----・8X1
0-"85-9...IXIG"' Table 7 - Discharge frequency machine: ILSaMHz Example 6 Using the manufacturing equipment shown in Fig. 10, boron (B) and carbon (
Using the content of 0) in the layer as a parameter, an amorphous layer having the layer structure shown in FIG. 7 was formed on the Aj cylinder to obtain an electrophotographic image forming member.

The preparation conditions for each layer region constituting the amorphous layer at this time are shown in Table 48 below.

Using each of the obtained electrophotographic image forming members, toner images were repeatedly formed on transfer paper by applying the same electrophotographic process as in Example 1, and the evaluations shown in Table 6 could be obtained. .

However, X(6) in Table 8 is as follows.

86-1----IXIO-' 86-2-■-
5X10-'86-3---I XI O'''
86-4-Song 5X10-'86-5----IXI
O” 86-6-Tune 2 Using the content as a parameter, an amorphous layer having the layer structure shown in FIG. 8 was formed on the cylinder to obtain an electrophotographic image forming member. The preparation conditions are shown in Table 9 below.

Using each of the obtained electrophotographic image forming members, an electrophotographic process was applied in the same manner as in Example 1, and when toner images were repeatedly formed on transfer paper, evaluations as shown in Table 186 could be obtained. done.

However, X(7) in Table 9 is as follows.

87-1...lXl0-' 87-2...
...5X10-'81-3・----IXIO-'
87-4...5X1'0-'1-5...
...-IXIG-''S 7-6-------2 X
10-'87-7...4X10-'87-
8・Song・8X 10-"87-9...1x10
-' 9th table imitation of electric horse scissors: 13.511MIh Example 8 Using the 10th aiIK marking circle manufacturing apparatus, an amorphous layer having the layer structure shown in FIG. 9 was formed on an A4 cylinder in a layer region (tPt , )) using each layer thickness of the one layer region ("1t*") as a parameter to obtain an electrophotographic image forming member.The conditions for creating each layer region constituting the amorphous layer at this time were as follows:
Using each of the 90 obtained electrophotographic image forming members shown in Table 10 below, toner images were repeatedly formed on transfer paper by applying the electrophotographic process in the same manner as in Example 1. We were able to obtain the following evaluations.

Table 10 1k t jll m Ill : 1346 Mlh
Table 11 Example 9 A manufactured member was obtained using the manufacturing apparatus shown in FIG. 10 and using the contents of boron (B) and carbon (0) in the layer as parameters.
At this time, the conditions for creating each layer region constituting the amorphous layer were as shown in Table 12 below, and the electrophotographic process was applied in the same manner as in Example 1 using the obtained nine electrophotographic groove forming members. When a toner image was repeatedly formed on the transfer paper, a stable and high quality toner transfer image could be obtained. According to the manufacturing procedure, an amorphous layer having the layer structure shown in FIG. 3 was formed on the Aj cylinder, and then a silicon carbide-based surface barrier layer was formed on the amorphous layer according to the following conditions. The electrophotographic process was repeatedly applied to the sample thus obtained in the same manner as in Example 1, and toner transfer images were obtained.The millionth toner transfer image was also of extremely high quality. Even when compared with the second transferred image, it was comparable in some respects.

Gas used...0)14 SiH4/He=10:250 flow Kaoru...-8iH4== 10500M flow rate ratio・
・・OH4/5iH4=30 layer formation speed...f84
A/sec Discharge power: 0.18 Substrate temperature: -250°C Reaction pressure: Q, 5 torr Example 11 Samples in Examples 4 to 7/+684-1 to 84-4゜85-1~85-9.86-1~86-6.87-1~
After forming an amorphous layer on the Aj cylinder under the same conditions and procedures as in Example 10, a silicon carbide-based layer was formed on each amorphous layer under the same conditions and procedures as in Example 10. 28 samples were prepared by forming a surface barrier layer (Sample A 811-1
For each sample obtained (~5ll-28'), a toner image was repeatedly formed on each predetermined transfer paper by applying the electrophotographic process in the same manner as in Example 1. quality.

0 Example 12 in which a toner image with a high resolution gI of 1 degree was obtained Using the manufacturing apparatus shown in FIG. 10, A-j An amorphous layer having the layer structure shown in the Kma diagram on the cylinder was formed, and the electrophotographic process was applied as in Example 1 and risJ using the obtained electrophotographic image forming member. When the toner ij* was repeatedly formed on the transfer paper, a stable and high quality toner transfer image 1 could be obtained.

Table 13 Discharge rate: 18.51M)b

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory diagram for explaining one preferred example of the structure of the photoconductive member of the present invention *tlc2 to a! FIG. 9 is a schematic explanatory diagram illustrating the layer structure of the amorphous layer constituting the photoconductive member of the present invention, and FIG. 10 is a diagram of the apparatus used for producing the photoconductive member of the present invention. Schematic explanatory diagram 0100...Photoconductive member 101...Support 102...Amorphous layer 103...First layer region 104...Second III region 105... Layer Area 1
06... Upper layer region 107... Free surface H value - Procedural amendment (voluntary) December 12, 1981 JL 21, Commissioner of the Japan Patent Office Shima 1) Haruki, Patent application filed on December 1, 1981 (4) ) No suffix 2, Name of the invention Photoconductive member 3, Relationship to the case of the person making the amendment Patent applicant address 3-30-2 Shimomaruko, Ota-ku, Tokyo Name (10
0) Canon Co., Ltd. Representative Kaku Ubazo 5, Subject of correction 9゛°1 (1
) Column 6 of the [Detailed Description of the Invention] of the specification: Make the amendment according to the content of the amendment. (b) Delete the sentences in lines 1 to 6 on page 23 of the specification. (2) Figures 5 and 6 of the drawings will be corrected as shown in the attached sheet. 7. List of attached documents X≧...each copy. (2) Drawings showing Figures 5 and 6 respectively...each -
General. The example shown in FIG. 4 is a modification of the example shown in FIG.
In a layer region (t+tB) in which carbon atoms are uniformly distributed and contained in a distribution concentration C(e)1, a layer region in which the 111'1lj1 atoms are uniformly fractionally contained in a distribution concentration C(to)1 This is the same as the case shown in FIG. 3, except that (t2tB) is provided. The example shown in FIG. 5 is a case in which there is a layer region in which group (I) atoms are contained at a distribution concentration Call5 even on the surface is. The amorphous layer of the example shown in FIG. ), there is a layer region (tlt2) in which group II atoms are uniformly contained but carbon atoms are non-uniformly contained, and a layer region (tlt2) in which both the carbon element f- and group II atoms are non-uniformly contained. Layer area (tBt
t). That is, the layer region (t2tB) containing carbon atoms is divided into a layer region (tzLs) which is substantially uniformly distributed in the layer thickness direction with a distribution concentration C1, and a layer region (tzLs) containing carbon atoms, which is gradually distributed from the distribution concentration Qc)1 to 8 It consists of a layer area ('5j2) which is typically reduced to virtually zero. In addition, the layer region (tstB) is a layer region (tstB) in which group (2) atoms are substantially uniformly distributed at a distribution concentration C1 from the support side.
aju), distribution concentration Cci@3 from distribution concentration C(g)l
The layer region ('ts
t+) has a stacked layer structure. FIG. 6 shows a modification of the example shown in FIG. In the case of the example shown in FIG. 6, there is a dependent region 1t (tztn) in which carbon atoms and the group ■ element r are uniformly distributed with distribution concentrations CQjt and C■, respectively, and carbon atoms have a distribution concentration C ( C)1
A layer region (tst2) whose concentration is gradually decreased linearly to reach substantially zero, and group (I) atoms are contained in the layer region (t8t2) in a distribution state which decreases linearly. A layer region (tlt2) and a layer region (tstl) substantially containing no group (I) atoms are provided. Table 5: Discharge frequency 713.56F11Hz, Table 7: Discharge frequency +t
3.56■h Written amendment (1 button 1. Display of the case 1982 Patent Application No. 194293 2, Name of the invention Photoconductive member 3, Person making the amendment Relationship to the case Patent applicant address Tokyo 3-30-2 Shimomaruko, Ota-ku Name (100
)Representative of Canon Co., Ltd. Ryu Kaku Ryu Mibu0 Agent Address: 3-30-25 Shimomaruko, Ota-ku, Tokyo 1413, Japan
Target of amendment N) "Detailed Description of the Invention" column of the specification] "Brief explanation of the drawings" column υ of the document, contents of the text (1) ■Page 13, line 13 of the specification "-111 usually 1 to 100-1--good" to "-m-usually 0.
01 to 5 X to' atomic ppm, preferably 1 to 100100 atomic ppm, more preferably. ■ On page 13, line 19 of the same page, change “if, -111 preferably----” to “if, 0.001 to 30 atoms
c%, preferably 0.01 to -111%, more preferably 1----J. ■ “--m-” on page 15, line 19 to line 20 of the same
Normal case---1000 atomic ppm,
``Preferably 1111'' is replaced with ``-111 normally,
0.1-8 x 104104ato ppm, preferably 0.1-1000atoiic ppm, more preferably ----'' correction. In the second line of page 16, the phrase ``--m- usually---1 suitably'' was replaced with ``-111 usually 0.01~35 a
tomic%, preferably 0.01 to 30 atomic%
c%, more preferably. ■ r---0,65~0.9 on page 47, line 4
5,----J is r---0,65~0.88,---
-- Correct as J. ■ r---0,85~0 on page 47, line 18.
88----J to r---0,82~0.88, --
Correct as −=J. ■ r on page 48, line 4---0,43~0.80
---0.43~0.50J r-0,40~0.57
---Corrected to 0.53 to 0.57J. (2) r1 on page 80, line 1O to line 11 of the specification
05---One-layer region J, rlOEi -1--Upper layer region" respectively r105--One upper layer region J,
rlo13---one free surface" and corrected as r10
7 - Delete "free surface".

Claims (1)

[Scope of Claims] Comprising a support for a photoconductive member and an amorphous material having silicon atoms as a matrix and containing at least either a hydrogen atom or a hydrogen atom as a constituent atom,
In a photoconductive member having an amorphous layer exhibiting photoconductivity, the amorphous layer contains carbon atoms as constituent atoms in a non-uniform and continuous non-uniform distribution state in the layer thickness direction. It is characterized by having a 10th layer region and a 20th layer region containing atoms belonging to group ill of the periodic table as constituent atoms in a non-uniform and continuous distribution state in the layer thickness direction. Photoconductive member (2) The first layer region and the second layer region share at least a part thereof [Photoconductive member 0 according to paragraph 1] (3) The first layer region and the second layer region share at least a part The photoconductive member according to claim 1, wherein the layer region and the second layer region are substantially the same layer region. (4) The second layer region is present in the first layer region. The photoconductive member Q (5) according to claim 1, wherein the layer region II- constitutes substantially the entire layer region of the amorphous layer. The photoconductive member according to (6) the photoconductive member according to claim 1, wherein the 20th layer region constitutes substantially the entire area of the amorphous layer (7) the 1st 0 The photoconductive member according to claim 1, wherein the distribution state of carbon atoms in the layer region forms a decreasing distribution on the side opposite to the side where the support is provided. Distribution pattern of longitudinal cable atoms in the 10th layer region l
The photoconductive member according to claim 1, which forms a highly distributed distribution on the i/Ii support side.