JPS58145953A - Photoconductive member - Google Patents

Abstract

PURPOSE:To improve durability, etc., by forming an auxiliary layer contg. N, a preventing layer for implantation of electric charge contg. atoms of group V of periodic table at the ratio in the specific relation with layer thickness (t), the 1st photoconductive layer and the 2nd photoconductive contg. C on a substrate and using Si as a base material for the respective layers. CONSTITUTION:An auxiliary layer 102 consisting of amorphous Si contg. N is formed on a conductive substrate 101, whereafter a preventing layer 103 for implantation of electric charge consisting of an amorphous Si layer contg. atoms such as P, As or the like of group V of periodic table at 30 atom ppm if the layer thickness (t) is >=30Angstrom and <0.3mu, and at >=30 atom ppm and <100 atom ppm if the (t) is >=30Angstrom is formed thereon. The 1st photoconductive layer 104 of amorphous Si is formed on the layer 103 and the 2nd photoconductive layer 105 of amorphous Si contg. C is formed thereon. A photoreceptor 100 having high adhesive power between the substrate 101 and the layer 103 and excellent durability, and electrical and photoconductive characteristics is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as light (here, light in a broad sense refers to ultraviolet light, visible light, infrared light, X-rays, and R-rays). Regarding.

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic forming member in the FI forming field, or a document reading device, it has a high sensitivity and a 8N ratio [light weight Ip].
/dark current (Id)], has fall yield spectral characteristics that match the spectral characteristics of the electromagnetic waves to be irradiated, has fast photoresponsiveness, has a desired dark resistance value, and has a high In addition, solid-state imaging devices must be cleaned up within a specified period of time due to pollution.
Characteristics such as being able to undergo K treatment are required. Particularly in the case of an electrophotographic forming member incorporated into an electrophotographic apparatus used in an office as a business machine, the above-mentioned non-polluting property during use is an important point.

Based on this point, amorphous silico 7 (resolved with a-8i after N) is a light guiding material that has recently attracted attention.
Publication No. 55718, ii.
In Rokukoku Publication No. 2933411, the [C- use for the Marugame conversion reading device is described.

However, a photoconductive member having a photoconductive layer made of conventional A-8I has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsivity, and usage environment characteristics. In terms of stability, stability over time, and durability, each of the characteristics has been measured in the direction of F, but there is room for improvement in terms of improving the overall characteristics. The reality is that

For example, when applied to an electrophotographic image forming member, if an attempt was made to simultaneously increase the light sensitivity and increase the dark resistance, it has often been observed in the past that residual W zones remain during use. When a conductive member is used repeatedly for a long period of time, fatigue accumulates due to repeated use, and there are many disadvantages such as a ghost phenomenon occurring.

In addition, when the photoconductive layer is composed of a-8i material, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive type Boron atoms, phosphorus atoms, etc. are included as constituent atoms in the layer of the light guide for control purposes, and other atoms are included in the light guide layer for the purpose of improving properties. In some cases, problems may arise in the electrical or photoconductive properties, voltage resistance, and durability of the formed nine layers.

That is, when used as an image forming member for electrophotography, for example, the lifetime of photocarriers generated in the formed photoconductive layer by light irradiation may not be sufficient, or charge may be injected from the support side in dark areas. If the prevention of
For example, a temporary image defect that is thought to be caused by a localized discharge breakdown phenomenon called ``white streak'' and a fixed image defect that is commonly referred to as ``white streak'' that is thought to be caused by rubbing when a blade is used for cleaning. was occurring. In addition, it is commonly said that Fl! is used in a humid atmosphere or used immediately after being left in a humid atmosphere for a long time. There were many cases where blurring of Iig& occurred.

- 1- When the thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support as time passes after it is left in the air after being pumped out of the vacuum deposition chamber for layer formation. This tends to cause phenomena such as cracks in the fi + -. This phenomenon occurs particularly when the support is excessively large, and often occurs in the case of the drum-shaped support used in the field of digital photography, which is a problem that cannot be solved in terms of stability over time. There is.

Therefore, while efforts are being made to improve the properties of the A-84 material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing light guide components.

The present invention has been made in view of the above points, and has the applicability and applicability of A-8I as a photoconductive member used in electrophotographic image forming members, solid state mechanical devices, reading order devices, etc. As a result of intensive research and consideration from this point of view, we found that silicon atoms are used as the base material, and zero hydrogen atoms or... rogen atoms (
Amorphous g material containing at least one of
a-8i (H, Not only does it exhibit excellent hardness and time running properties, but it also outperforms conventional light guide components in every respect. Based on nine findings, it has been found that it has particularly excellent properties as a photoconductive member for electrophotography.

The present invention provides electrical, optical, and photoconductive properties to the usage environment.
It is virtually always stable without any dependence, has excellent resistance to light fatigue, shows no deterioration even after repeated use, has excellent durability and moisture resistance, and almost no residual residue is observed. The main objective is to provide a complete range of photoconductive members.

The purpose of the pond of the present invention is to have excellent tightness between each layer of the laminated layers (provided on the support) and the support, and to be dense and stable in terms of structural arrangement. The object of the present invention is to provide a photoconductive member with high layer quality.

Another object of the present invention is that when A is used as a self-forming member for electrophotography, it has a sufficient charge retention ability during the thermal processing for forming an electrophotographic structure, and the ordinary soldering method is extremely effective. An object of the present invention is to provide a photoconductive member having excellent magnetophotographic properties that can be applied to.

Another object of the present invention is to provide a round groove (member) for electrophotography that can easily obtain high-quality images with high density and clear contrast and high resolution. The goal is to provide the following.

The photoconductive member of the present invention is composed of a support for the photoconductive member, an amorphous material containing silicon atoms as a matrix and nine element atoms as constituent atoms, a nine auxiliary layer, and a silicon f1i
, a charge injection prevention layer made of an amorphous material containing atoms belonging to Vt1k of the Printing Period Table as its constituent atoms, and an amorphous material containing silicon atoms as its parent, a first amorphous layer exhibiting conductivity; a second amorphous layer provided on the amorphous layer and made of an amorphous material containing silicon atoms and carbon atoms as constituent atoms; 0.3 when the thickness type of the charge injection prevention layer is 30λ or more
The tC(V) of the atoms belonging to the fifth column of the periodic table contained in the charge injection prevention layer is 30 a
atomic- or more, or t is 301 or more and C(7) is 30 atomic P or more and 10
It is characterized by being less than Q atomicgm.

The photoconductive member of the present invention, which is designed to have a similar layer structure, can solve all of the above-mentioned problems and has extremely excellent electrical and optical properties.

Indicates photoconductive properties, pressure resistance, and usage environment characteristics.

In particular, the first electrode applied as a scratch-forming member for electrophotography has no influence of residual potential on scratch formation, its electrical characteristics are stable, and it has a high sensitivity of seconds (C, %SN ratio). It is a high-quality image with excellent light fatigue resistance, good reversal use characteristics, sharpness in #, clear appearance of no-futo/, and high resolution. ! It can be obtained stably and repeatedly.

The photoconductive member of the present invention also has an amorphous structure formed on the support.
The fibers themselves are strong and have excellent adhesion to the support, and can be repeatedly used at high speed and continuously for hours.

Hereinafter, the photoconductive member of the present invention will be explained in detail with reference to the drawings.

FIG. 1 is a four-type structural diagram schematically shown to explain layer supplementation of a photoconductive member according to a first embodiment of the present invention.

The photoconductive member 100 shown in FIG. 1 includes a support 101 for use as a photoconductive member, an auxiliary layer 102, an electrical press-in prevention r4103, and a first amorphous material having photoconductivity +m (
I) 104, a second amorphous '4 composed of an amorphous material (hereinafter referred to as "m-8ixC1-xJ") whose constituent atoms are silicon atoms and carbon atoms (1) Ios, The amorphous layer (1) 105 has a free table [1i106.

The auxiliary layer 102 is mainly provided for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103, and has affinity with one direction of the support 101 and the charge injection prevention layer 103. It is made of materials that will be described later.

The charge injection prevention layer 103 mainly has the function of effectively preventing charge from being injected into the amorphous layer 104 from the support 101 side.

Amorphous 4 (I) 104 Fi mainly has the function of generating photocarriers in lli;liT@104 upon irradiation with sensitive light and transporting the photocarriers in a predetermined direction.

The amorphous layer (1) 105 is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability.

The auxiliary layer in the photoconductive member of the present invention is made of an amorphous material (having silicon atoms as a matrix, 91g atoms as constituent atoms, and optionally hydrogen atoms (H) and halogen atoms (4)). Hereafter, it is composed of [arranged as a-8IN(H,X)J].

a-SiN(H,X) is a silicon atom (81)
An amorphous material (hereinafter referred to as ra5jaNs-aJ) whose entire base is nitrogen atoms (N) and whose constituent atoms are silicon atoms (8I), nitrogen atoms (N) and hydrogen atoms (H) Amorphous material as constituent atoms (hereinafter referred to as “a-(S
'bN+-b)cHt-cl), silicon atom (
81) as the base, nitrogen atom (N) and halogen atom (X
) and optionally hydrogen atoms () () (hereinafter referred to as r a-(8idN1-d)e(H-
X) t −6J).

In the present invention, the halogen atoms (X) contained in the auxiliary layer as necessary include fluorine, chlorine,
Preferred examples include 9M bromine, particularly fluorine and chlorine.

In the case where the auxiliary nozzle is composed of a single amorphous material, examples of forming methods include glow discharge method, sputtering method, ion implantation method, ion blating method, and electron beam method. These manufacturing methods are manufacturing conditions.

Equipment capital investment load 8f, manufacturing scale 9 manufactured light guide'
(Factors such as properties desired for the member are selected and adopted as appropriate, but in addition to silicon atoms, nitrogen atoms are The glow discharge method or the sputtering method is preferably employed because of the advantages that atoms, hydrogen atoms or halogen atoms if necessary, can be easily introduced into the auxiliary layer.

[K. In the present invention, the auxiliary layer may be formed by using a glow discharge method and a sputtering method in the same system. By glow emission vL method, a-8iN(H,X)
In order to form the auxiliary layer consisting of, basically, a raw material gas for supplying 8i that can supply silicon atoms (8i), a raw material gas for introducing nitrogen atoms (N), and hydrogen as necessary. F′i/ and halogen atom (X
) Kyoshina gas for introduction is introduced into a deposition chamber whose interior can be reduced in pressure to generate a glow discharge in the single-core deposition chamber, and a- 8
It is sufficient to form an auxiliary layer made of iN(H,N).

For example, when forming the auxiliary layer by sputtering, it is done as follows.

Firstly, when sputtering a target made of SL in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, nitrogen atoms (
N) Hydrogen atoms ( ) (
) and ii/ and the raw material gas for introducing halogen atoms (X) into a vacuum deposition chamber where sputtering is performed.

The second part contains a target for sputtering and 1.
By using a target composed of i, N, or a target composed of Si and a target composed of 8i, N, or a target composed of Fi8i and Sl, N4. Nitrogen atoms (N) can be introduced into the auxiliary layer formed. At this time, if both sets of raw material gases for introducing nitrogen atoms (N) are used together, the flow rate can be controlled to introduce nitrogen atoms (N) into the auxiliary layer.
It is easy to set the amount of N) to an arbitrary value.

The content of hydrogen atoms (N) introduced into the auxiliary layer can be determined by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing nitrogen atoms (N) is introduced into the deposition chamber. The proportion of nitrogen atoms (N) contained in the target for introduction can be arbitrarily controlled as desired by adjusting the proportion of nitrogen atoms (N) contained in the target for introduction, or by doing both.

The starting materials used as the raw material gas for supplying 8j used in the present invention include 81 crosspiece, 811) (@, 8t
3H@ *8ij4. Silicon hydride (silanes) in a gaseous state or that can be gasified, such as . (4,8i and crosspieces are preferred.

If these starting materials are used, H together with Si can be formed in the auxiliary layer formed by appropriately selecting the layer forming conditions.
can also be introduced.

Effective starting materials that serve as raw material gas for supplying Si include:
In addition to the above-mentioned silicon hydride, silicon compounds containing halogen atoms (X), so-called halogen atom-substituted silane flange conductors, specifically, for example, 5ir4.5itF', 5
Preferred examples include silicon halides such as iCt4.8iBr, and 1N! are SiH, F,
, 8iH,I, , 8iH,Cz, , 8iH
Cz, , SiH, Hr, .

5i) Halogenated silicon hydrides such as IBr, etc., gaseous or gasifiable halides having a hydrogen atom as one of their constituents are also mentioned as starting materials for supplying S+ for the formation of an effective auxiliary layer. I can do things.

When using these silicon compounds containing halogen atoms (X), it is possible to introduce X together with SI into the auxiliary layer formed by appropriately selecting the layer formation conditions. A silicon halide compound containing a hydrogen atom in the 9-stage proboscis is characterized by the introduction of a hydrogen atom into the 1 when forming an auxiliary layer, and at the same time a hydrogen atom which is extremely effective in controlling electrical or charge characteristics. Since (H) is also introduced, it is used as a suitable starting material for introducing the halogen atom (X) in the present invention.

In addition to the above-mentioned materials, examples of effective starting materials for the raw material gas for introducing the halogen atoms (X) used to remove Vr to form the auxiliary layer in the present invention include fluorine, chlorine, bromine, and iodine. Rogen gas, BrF, C/F,
C/F,, BrF,, BrF,, IP,, IP
,.

IC/, IBr, etc...rogen-related compounds, HF
, HC/.

) fBr, HI, etc. Hydrogen halogenide i can be mentioned.

The raw material gas for introducing the phoneme atoms (5) used when forming the auxiliary layer (the starting material that can be effectively used is a relative having N as a constituent atom!→L) For example, nitrogen (Nl) as a constituent atom.

Ammonia (NHs), hydrazine (HeNNH*)
, hydrogen azide (HNa), ammonium azide (NH4
Mention may be made of gaseous or gasifiable nitrogen such as Nm), nitrogen compounds such as sulfates and azides.

In this song, halogen atoms such as nitrogen trifluoride (FsN) = nitrogen tetrafluoride (F+Nt) can also be introduced by replacing 9 with 7J] to introduce an elementary atom (N) and introducing a halogen atom (X). W table compounds can be mentioned.

In the present invention, the diluting gas used when forming the auxiliary layer by the glow discharge method or sputtering method is as follows:
So-called rare gases, such as He.

O Ne, Ar, etc. can be mentioned as suitable ones. a −8i N (H,
), the function of the auxiliary layer is to strengthen the adhesion between the support and the charge injection prevention 1-, and to uniformly maintain electrical contact between them. The auxiliary layer is carefully selected and its manufacturing conditions are strictly selected so that the properties required for the auxiliary layer are imparted as desired.

a-8iN(H) with properties suitable for the purposes of the present invention.

Important g in the layer creation conditions for forming auxiliary 1- consisting of X)! One example of this is the temperature of the support during layer formation. That is, the surface of the support t*1Ka-8iN(H
When forming the auxiliary layer consisting of , The temperature of the support during layer formation is strictly controlled so that a -8iN(H,X) having the following properties can be formed as desired. In order to effectively achieve the purpose of the present invention, the optimal range of the support temperature when forming the auxiliary layer is selected as appropriate in accordance with the method of forming the auxiliary layer, and the formation of the auxiliary layer is carried out. However, in normal cases, the temperature is 50°C to 350°C, preferably 100°C to
It is desirable that the temperature be 250°C. To form the auxiliary layer, it is necessary to continuously form the auxiliary layer, the charge injection prevention layer, the amorphous layer, and even other layers formed on the amorphous layer as necessary in the same system. The use of glow discharge method and sputtering method is advantageous because it is relatively easy to control the composition ratio of atoms constituting each layer and control the layer thickness7 compared to other methods. However, when forming an auxiliary layer using these layer forming methods, the discharge power and gas pressure during formation are important, as well as the support temperature mentioned above, as they influence the characteristics of the auxiliary layer created. This can be cited as a major factor. The discharge power conditions for effectively creating an auxiliary layer with good productivity in order to achieve the purpose of the present invention are usually 1 to 300 W, preferably 2 to 15 W.
It is 0W. Father, the gas pressure in the deposition chamber is usually 3X104 ~
5'r'orr1 preferred ic t'i 8 X 10-
” It is preferable that it be about -0.5 TOrr.

4' The amount of nitrogen atoms contained in the auxiliary layer in the photoconductive member of the invention and the amount of hydrogen atoms and halogen atoms contained as necessary are determined according to the method of the present invention, as in the preparation of the auxiliary layer. The objective tl - the desired characteristics to be achieved is an important factor in forming the aid 1 -.

]1 Amount of % Mmp (N) contained in the auxiliary r-, water Jl
1 and the amount of halogen atoms in the element (H), respectively, in accordance with the above-mentioned I-Creation Article 14:
However, it can be determined arbitrarily according to the user's wishes.

When the auxiliary layer is composed of a-8i1N1-1,
The content of nitrogen atoms in the auxiliary layer is preferably 1×10'
~60 atomic%, more preferably 1-50
In terms of atomic%, a is preferably 0.4 to 0.
99999.

More preferably, it is 0.4 to 0.99.

a (8sbN1 b)cHt-c, the nitrogen atom (N) content is preferably FilX
l 0 (~55 atomic X, more preferably 1-55 atomic, the content of hydrogen atoms is preferably Fi 2-35 atomic
If expressed as c, b is usually 0.43 to 0.999
99, more preferred KFi0.43-0.99. C is usually 065-098. Preferably α7 to 0.95, a C8”dNt-d)e(HLX)
In the case of t −e , the nitrogen atom content t is
Preferably I X 10' to 60 atomic X,
More preferred is 1 to 60 atomlc%.

The content of halogen atoms or the amount of dead metal in combination of halogen atoms and hydrogen atoms is preferably #″i1 to 20 ato
mic %, more preferably 2~l 5 atomic
%, and the hydrogen atom content t in this - combination is preferably 19 atomicX to F1, and more preferably l 3 at
ornic% or less.

If expressed as d and e, d is preferably u 0
．． 43-0.99999, more preferably 0.4
3-0.99. c is preferably 0.8 to 0.9
9. More preferably, it is 085 to 0.98.

In the present invention, the I-thickness of the auxiliary layer constituting the photoconductive member may be determined as appropriate depending on the thickness of the charge injection prevention layer provided on the auxiliary layer and the characteristics of the charge injection prevention layer. It is determined.

In the book @ Ming, the thickness of the auxiliary layer is 3.
0A to 2μ, preferably 40i to 1.5711, optimally 50μ to 1.5s.

The charge injection prevention +4 constituting the photoconductive member of the present invention has a non-conductive atom (8i) as a parent body, and is based on the periodic law &MVjlkK.
) 14 (group IiV atoms) and preferably a hydrogen atom (H) or a halogen atom (X), or both of them (hereinafter referred to as "a-84(v,
H,

In the present invention, the layer thickness of the charge injection prevention layer and the content of group (I) atoms (tcCv) are more preferably 40 μm≦
t < 0.3 μ and C(V) is 40 atoms
c- or more or 40 atoms ≦CCv
I < 10° atomic- and the current is 40 A or more, maximum A K i,i, 5° t < 0.3 s, and c
(V) is 5 Q mtomicgm or more, or so atomcm ≦c(V) < 10910
9ato- and t is preferably 50A or more.

In the present invention, atoms belonging to Group V of the periodic table contained in the charge injection prevention layer include P (phosphorus), As (arsenic), Bi (bismuth), etc. Among them, P and S are particularly preferably used.

Formation of a charge injection prevention layer composed of a-8i (V, H, A vacuum deposition method that utilizes this phenomenon is adopted. For example, according to the glow discharge method V, a-8i (V
, H, A raw material gas for introducing group atoms, and a raw material gas for introducing hydrogen atoms (0) if necessary, and a raw material gas for introducing halogen atoms (X) are introduced into a deposition chamber whose interior can be made to have a reduced pressure t,, -'c
, a glow discharge is generated in the deposition chamber, and +fF is preliminarily applied.
It is sufficient to form a mesh consisting of a-8i (V, H, In addition, when forming by a sputtering method, when performing whole sputtering on a target composed of a non-containing gas such as Ar or He, or a mixed gas based on a gas of this type, V. It is a shame to introduce the raw material gas for introducing group atoms into the deposition chamber for sputtering together with the gas for introducing hydrogen atoms (H) and hydrogen atoms (X) as necessary.

In the present invention, the starting materials that serve as the raw material gas used to form the charge injection prevention layer are the same as the starting materials for forming the auxiliary layer, except for the starting material that serves as the raw material gas for introducing group (III) atoms. One is selected and used as desired.

In order to structurally introduce Group Ⅰ atoms into the charge injection prevention layer, r-formation @KgV! It is possible to introduce the starting material for introducing +I atoms into the deposition chamber in a gaseous state together with other starting materials for forming the charge injection prevention layer. As the starting material for such introduction of Group (I) atoms, it is desirable to employ materials that are gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

Specifically, starting materials for introducing tsv group atoms include PH, )', f'' (4 etc. c
v hydrogenated oss Pl (4It pp, PFse
PC/st PC/,, PHr,.

Examples include phosphorus halides such as PBr, PI, and the like.

In addition, AsH,, AsF, , ASC/, , A
sHr,, AsF,, 5bl(,.

8bF, , 8bF, , 8bC/, , SbC/
, , BiH, , Bier, , Bier.

etc. can also be mentioned as starting materials for introducing Group V atoms.

In the present invention 11C, in order to provide charge injection prevention characteristics, 4
The Group V atoms contained in the #J press-in prevention layer are substantially parallel to the layer thickness direction of the charge injection prevention layer (in a plane parallel to the surface of the support) and in the layer thickness direction. , preferably substantially uniformly distributed.

In the present invention, the content of group (III) atoms introduced into the charge injection prevention layer is determined by the gas flow rate, gas flow rate ratio, and discharge power of the starting material for introducing group (III) atoms that is introduced into the deposition chamber. , support f! It can be arbitrarily controlled by controlling the temperature, pressure in the deposition chamber, etc.

In the present invention, examples of the halogen atom (X) that may be contained in the charge injection prevention layer if necessary include the same halogen atoms (X) as described in item 9 in the explanation of auxiliary No.

In the present invention, in order to form the amorphous layer (I) composed of "-8'(H6X)", #i, for example, a glow brazing method, a sputtering method, or an ion silating method, etc. is used. For example, a-8i (H,
) to form an amorphous layer consisting of basically #i/ and .・A raw material gas for introducing rogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber to cause Ka It is sufficient to form 1 consisting of −8i(H,X).

In addition, when forming by sputtering method, KFi, such as A
When sputtering a target composed of an inert gas such as r, He, or a mixture of these gases in an atmosphere of 9-temperature gas, hydrogen atoms (H) or /) J and halogen atoms (X) are sputtered. Deposition for sputtering gas for 4 people ii! If you introduce it to

In the present invention, as the halogen atom (X) contained in the amorphous +@1 (I) depending on the necessary IK, the same halogen atoms (X) as mentioned in the case of the auxiliary layer can be mentioned.

In the present invention, the raw material gas for S1 supply that is conveniently used to form the amorphous layer (I) is 98 tl ( 4*8
'tF'449 For S-, gaseous or gasifiable silicon hydride (silanes) such as S-mass 0 can be cited as one that has been effectively used, especially for ease of handling in layer creation work. In terms of 8i supply efficiency, etc., 51) (4 * S4
1 is preferred.

As in the case of the auxiliary layer, many halogen compounds are effective as the raw material gas for introducing halogen atoms used in forming the amorphous layer (I) in the present invention.
For example, halogen gases, halides, interhalogen compounds, halogen-substituted silane compounds in a gaseous state or gasified E7 are preferably mentioned. Kite-f
(X) constitutes l! In the present invention, silicon compounds containing halogen atoms, which are in a gaseous state or can be gasified, can also be mentioned.

In the present invention, the conductive properties of the amorphous layer (I) can be arbitrarily V-controlled as desired by containing a substance that controls the conductive properties.

Examples of such substances include impurities referred to in the field of medium conductors, and in the present invention, a-8i (H, ), a P-type impurity that gives pH conductive properties, specifically KF′i
, atoms belonging to the first ts of the periodic table (group Ⅰ atoms), for example, B (boron).

There are u (aluminum), Ga (gallium), In (I/dium), T/(thallium), etc., and B and Ga are particularly preferably used.

In the present invention, the content of the substance that controls the conduction properties contained in the amorphous layer (I) is determined by the conduction properties required for the amorphous layer (I) or Vi1n(I). The properties of the other layer provided in direct contact with the layer, the relationship with the properties of the contact interface with the other layer, etc. can be selected as appropriate in terms of organic clarity.

In the present invention, ato+ contained in the amorphous layer (I)
It is desirable that it be n1c-.

Amorphous! - In order to structurally introduce a substance that controls conduction properties, for example, group Ⅰ atoms, in addition to layer formation, a starting material for introducing ＠ group atoms is added in a gaseous state to the deposition chamber in an amorphous form. It may be introduced together with other starting materials for forming -.

As a starting material for the introduction of Group 1 I atoms, one that can be used is one that is gaseous at normal pressure, or at least easily gasified under layer-forming conditions. Delicious.

Specifically, as a starting material for introducing such a group atom, Bm[L, B4Hn.

I(s"4 * 'I"He B,)'l16 t'
Boron hydride such as H14 to At*, Bl', , BC
Examples include halogenated halides such as f, , BBr, and the like. In addition, AIces * GaC/Hatake, Ga (C
M), IoC/s *T/C/1, etc. can also be mentioned.

In the present invention, the amount of hydrogen atoms (H) contained in the charge injection prevention layer and the amorphous layer (I) of the photoconductive member to be formed or the breakage of Rogge/atom (X) or water #atom The sum (H-1-x) of the amounts of (H) and...rogen atoms (X) is usually 1 to 40 atOmic X, preferably 5 to 30
It is desirable to make it atomic.

K, which controls the amount of hydrogen atoms (H) and/or I/rogen atoms (X) contained in the amorphous layer (I), is, for example, the support material III degree or/and Hydrogen atom (
The amount of the starting material used to contain H) or I/Rogen atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled.

In the present invention, the dilution gas used when forming the amorphous layer (I) by the glow discharge method or the sputtering gas used when forming the amorphous layer (I) by the sputtering method is #I1m gas. , for example He, Ne,
Preferred examples include Ar.

In the VC of the present invention, as the layer thickness of the amorphous layer (I),
It is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but it is usually 1-100μ, preferably 1-80μ, and most preferably t-i 2-50μ. It's a good thing.

In the photoconductive member of the present invention, the first amorphous*m(1)
The second amorphous layer (1) provided in h is separated from the amorphous layer (I) and the second amorphous! A common configuration II in which each of the amorphous materials forming the l (1) is a silicon atom
Since it has an element, chemical stability can be sufficiently ensured at the laminated interface.

The formation of the 20th amorphous layer (1) composed of a 5txC,z is performed by sputtering method, ion planing method, ion, pooping method, nicktron beam method, etc. will be accomplished. These bond laws are based on manufacturing conditions,
It is selected and adopted as appropriate depending on factors such as the load of equipment capital investment, Me scale, and the desired characteristics of the photoconductive member to be manufactured, but the manufacturing conditions for manufacturing the photoconductive member with the desired characteristics are The sputtering method, the electron beam method, and the ion blating method are preferably used because they are relatively easy to control and can be easily introduced into the intermediate layer in which carbon atoms are fabricated together with silicon atoms. Ru.

In order to form the second amorphous material by the sputtering method, a single crystal or polycrystalline Si wafer and a C wafer, or a wafer containing a combination of 84 and C is used as a target, These may be performed by sputtering in various gas atmospheres.

etc. (')
I wafer and C wafer fx battering is sufficient.

Also, separately, one target with 81 and C heated is 1
By using e, it is introduced into a gas equipment system for sputtering and sputtering is performed in the gas atmosphere. When using the electron beam method, single-crystal or polycrystalline AM1/recon and high-purity graphite are placed in two #deposition boats, and each is independently co-deposited by an electron beam, or the same deposition boat is used. Silicon and graphite may be deposited using an electron beam at a desired mixing ratio under internal pressure. In the former case, the content ratio of silicon and carbon contained in the second amorphous layer is controlled by changing the accelerating voltage of the electron beam to silicon and graphite; , controlled by determining the amount of silicon and graphite mixed in advance. When using the ion blating method, a cypress gas is introduced into the vapor deposition tank, a high-frequency electric field is applied to a coil placed around the cypress tree, and a glow is generated. All you have to do is evaporate it.

The second amorphous layer (II) t-1 in the present invention is carefully formed so that the required properties are as desired.

In other words, substances whose constituent atoms are Si and C take on forms ranging from structural -C#i crystals to amorphous depending on the conditions of their creation, and electrically and physically ranging from conductive to semiconducting to insulating. In the present invention, a-8iz (4X
The selection of conditions for forming it is made strictly according to one's desire.

For example, in order to provide the second amorphous 4(I) with the main purpose of improving pressure resistance, a-8ixC1 is prepared as an amorphous II material with remarkable electrically insulating behavior in the usage environment. be done.

In addition, when the second amorphous layer (II) is provided for the purpose of improving the continuous aM, the use characteristics and the use environment characteristics, the above-mentioned electric heat dissipation is alleviated to some extent. , a8'Xcl-x is created as a eutectic material with a seed-like sensitivity to the irradiated light.

When forming 42 amorphous layers (seals) consisting of a5IXCI-X on the surface of the first amorphous (I), the temperature of the support during layer formation depends on the structure of the formed particles and This is an important factor that determines the properties, and in the present invention, -C1 and a-8i) having the desired properties are It is desirable that the temperature be tightly controlled.

The temperature of the support when forming the 20th amorphous layer (rei) in order to effectively achieve the purpose of the present invention is determined by the method of forming the second amorphous layer (rei) Km In addition, a suitable wax field is selected as appropriate to form the second amorphous Im(1),
The temperature is preferably 20 to 300°C, most preferably 20 to 250°C.

For the formation of the second amorphous layer, delicate control of the composition ratio of atoms constituting the layer and control of the thickness are relatively easy compared to other methods. Although it is advantageous to adopt the sputtering method or the electron beam method, when forming the second amorphous layer (seal) using these layer forming methods, the layer forming method should be adjusted in the same way as the support temperature described above. It can be cited as one of the important factors that influences the characteristics of the 1st, cl-x, in which the discharge power is generated.

a- having the characteristics for achieving the object of the present invention;
The discharge power conditions for effectively producing 81XC@-1 with good productivity are F'150W to 250W.
, the optimum value is preferably 80W-150W.

In the present invention, the preferable numerical ranges of the support am and discharge power for forming the second amorphous layer (layer) include the values in the ranges described above. are not determined independently and separately, but are mutually organic relationships such as a-8ix of desired characteristics KM,
, v to determine the optimum value of each layer creation factor.

Second amorphous layer (1) K in the photoconductive member of the present invention
The amount of carbon atoms contained is the second amorphous ij1m(1)
Similar to the preparation conditions for I-, it is an important factor in the formation of I-, which provides the desired properties to achieve the objects of the present invention.

In the present invention, the second amorphous 'm(1)K-containing matrix is composed of silicon atoms and carbon atoms (VCn).
L te as usual u, I X I O'-9Q mto
mi(~, preferably 1~80 a heavy orli(X, optimally 1ilO~75 atomic~. That is, if it is displayed on the previous page a-8ixC1-x, X is usually 01 to 0.99999, preferably 02 to o, 99, and preferably 025 to 0.9.

According to the numerical range t of the layer thickness of the second amorphous layer (seal) in this case #4, F9'r is set so as to effectively achieve the object of the present invention.
It can be determined as desired depending on the purpose of 14A.

Also, ll11 of the second amorphous layer (1) is the amount of carbon atoms expressed in the layer (seal) and the first amorphous layer (I).
The relationship with the "- storage" also needs to be determined as desired based on the organic relationship depending on the characteristics required for each type of operation.

In addition, it is desirable to take into consideration productivity and mass production as well as economic efficiency.

The film thickness of the second amorphous material (1) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 20μ.
It is desirable that the range is between 0 and 10μ.

The support used in the present invention is electrically conductive and
h It may be electrically insulating. As a conductive support,
For example, NiCr, stainless steel.

A/, Cr, Mo, Au, Nb, Ta, V, Ti, P
Metals such as T, Pd, etc., or alloys thereof can be mentioned.

Polyester is used as an electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinyl chloride/polystyrene and polyamide, and glass.

Ceramic and paper bags are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and it is desirable that the conductively treated running surface rkUM is provided with another layer.

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

A/, Cr, Mo, Mu, Ir, Nb, T
a, V, Ti, Pi, Pd.

Irs, 0. ,5n(), ,ITO(In,0
．． Conductivity is imparted by providing a film made of + SnO, ), etc., or a synthetic resin film such as a polyester film A -? l' Attba, Nt C
r t Mo Ag e Pb * Zn w N i
*Au*(:r, Mo, Ir, Nb, Ta, v
, Ti, Pt, or other thin metals are applied to the surface by evaporation, beam evaporation, or sputtering, or the surface is laminated with the metal, and conductive in the -Ji direction. Attachment 4 is given.The shape of the support -C is cylindrical.

It can be in any shape such as a belt shape or a plate shape, and can be shaped as desired.-C1
Its shape is determined, but if you keep it,
If the member 100 is to be used as a flaw forming member for electrophotography, it is preferably in the form of an endless belt or a cylinder in the case of continuous high-speed copying. The thickness of the support is 4
It is determined as appropriate to engrave the photoconductive member on the street, but if the photoconductive member is required to have the character of a town monument, it is possible to engrave it as long as it fully functions as a support. made as thin as possible. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., it is usually 10μ.
This is considered to be the above.

FIG. 2 shows one configuration of a preferred embodiment of the photoconductive member pond of the present invention.

The photoconductive member 200 shown in FIG. 2 is different from the photoconductive member lOO shown in FIG. It is to have.

That is, light guide 'III! The member 200 includes a support 2011 laminated in order on the support 201, and a lower support t! ! 2
02° Charge injection prevention layer 203. Upper auxiliary 11204,
a first amorphous layer (I) zi:is and a second amorphous layer (1) 206, the amorphous layer (1) 206
#i has a free surface 207. The northern auxiliary layer 204 is
The adhesion between the charge injection prevention layer 203 and the amorphous -tL+-(I) 205 is strengthened to ensure uniform electrical contact at the contact interface between both layers, and at the same time, the charge injection prevention layer 203 is
1 above 03 - electric sound is strong.

The 'Fs auxiliary layer 202 and the partial auxiliary layer 204 constituting the photoconductive member 200 shown in FIG. The materials are formed using similar layering procedures and conditions so that similar properties are observed. The charge injection prevention layer 203 and the amorphous layer (Ffl (1) 205 ) and the amorphous layer (layer) 206 are also formed of the charge injection prevention layer 103 and the amorphous layer (1) 104 shown in Structure 1, respectively. Amorphous 41 (1
) It has the same characteristics and functions as 105, and is formed by the same bite making procedure and conditions as in the case of FIG.

Next, a method of manufacturing the nine conductive portions produced by the vacuum deposition apparatus shown in Fig. 3 will be described.

Each of the gas cylinders 311 to 315 in the figure is sealed with a gas used to form the present invention. Gas (pure 1 Jj 99.999%, hereinafter abbreviated as SiH, /He) was placed in 8 dishes, and PH, gas (#! Real 99.999N, hereinafter abbreviated as PH, /He) diluted in a cylinder 312 was placed in a cylinder 312. ) F4 gas (pure [99,99, hereinafter abbreviated as 81F4/He) diluted in the cylinder 313Kt'i, NH,
The cylinder 315 is filled with gas (with a purity of 99.999), and the cylinder 315 is filled with a gas (with a purity of 99.999N). It goes without saying that the type of gas filled in these cylinders may be changed as appropriate depending on the type of layer to be formed.

KFi that makes these gases react 301 K 41 people
Make sure that each pulp 331-335 of the gas zenpe 311-315 and the leak pulp 306 are closed, and also that the inflow pulp 321-325.1 and the output pulp 326-
Step 330: After making sure that the auxiliary pulp 341 is open, first open the main pulp 310 to exhaust the reaction chamber 3011 and gas piping. Next, when the depth of the JkT9 total 342 reaches approximately 5 x 10 torr, the auxiliary pulp 341. Close H outlet valves 326-330.

After that, the pulp of the gas pipe connected to the gas cylinder to be introduced into the reaction chamber 301 is operated as specified in 1. hand,
A desired gas is introduced into the reaction chamber 301.

Next, an outline of an example of manufacturing a light guide wax member having the structure shown in No. 11yJK will be described.

Gas cylinder 311, Su8i H4/He gas, NH gas from gas cylinder 314, valve 331, respectively.
, 339 and outlet pressure gauge 336 . 339 respectively to lK#/cd, then gradually open the inlet valves 321 and 324, respectively, and mass flow controllers 316. 319 respectively. Subsequently, the outflow valve 326. 329. The auxiliary valve 341 is gradually opened to allow each gas to flow into the reaction chamber 301. At this time, the outflow valve 326° 32
Open the opening of 9, and the pressure inside the reaction chamber is the desired value yc.
Adjust the opening of the main valve 310 while looking at the vacuum gauge 342 and the Q gun.

Then, OiA#lt of the support body 309 is connected to the heater 30
After confirming that the temperature is set at 50 to 400 degrees Celsius (step 8), the power source 340 is set to the power of the shield part to generate a glow discharge in the reaction chamber 301, and the temperature is maintained for a desired period of time. A glow discharge is maintained to create an auxiliary layer of the desired layer thickness on the support.

The charge injection prevention layer can be formed on the auxiliary layer in the following manner, for example.

After the formation of the auxiliary layer is completed, 1ml 1343 is turned OFF'F' to stop the discharge, and once the valves of the entire system of gas introduction piping of the apparatus are closed, the gas remaining in the reaction fi 301 is discharged to the outside of the reaction chamber 301. Evacuate to achieve the specified vacuum level.

After that, /He gas is supplied to 8i from the gas conduit /pe 311, and P H, /He gas is supplied from the gas cylinder 312 to the conduit 331. 332 and outlet pressure gauge 336;
337 respectively, and gradually open the inflow valves 321 and 322, respectively, to flow into the mass flow controllers 316 and 317.Subsequently, the outflow valves 326 and 327, and the auxiliary valve 34
1 is gradually opened to allow each gas to flow into the reaction chamber 301K.

SiH4/He gas flow rate and PH1/He at this time
Outflow and cool so that the ratio of gas flow rate is the desired value.

327, and make sure that the pressure inside the reaction chamber reaches the desired value! While checking the reading of St 342, open the main pulp 310 to 1111 m. and support 30
It was confirmed that the temperature of 9 was set at one time in the range of 50 to 400°C by the heating heater 308 f, '4
Setting the source 343 to a desired power to generate glow discharge in the reaction chamber 301, maintaining the glow discharge for a predetermined time,
The desired layer thickness is formed as 4J: (assistance of solder injection prevention+Fl-).

The first amorphous 4(I) is formed using, for example, 8iH4/He gas filled in the cylinder 311, and F9
15L9 The same method as in the case of the auxiliary layer and the charge injection prevention layer l1
This can be done using m1.

In addition to Si/He gas, the raw material gas species used in forming the first amorphous layer (I) include, in particular, 8i, )(,
/He gas is effective in improving the layer formation rate.

The second amorphous layer (seal) can be formed on the first amorphous layer (I), for example, as follows. First, shutter 20
Open 5. All gas supply valves are once closed, and the reaction chamber 201 is evacuated by fully opening the main loop 210.

High-purity silicone 204-1. A target is provided in which high-purity graphite Ueno 5204-2 is installed at a desired area ratio. A gas is introduced into the reaction chamber 201 from the gas cylinder 215, and the main pulp 210 is heated so that the internal pressure of the reaction chamber 201 becomes 0.05 to 1 torr.
Adjust. The second amorphous layer (1) can be formed on the first amorphous layer (I) by turning on the high voltage power source and simultaneously sputtering the target.

When halogen atoms (X) are contained in the auxiliary layer, the charge injection prevention layer, and the first amorphous layer (I), for example, 8iF4/He is added to the gas used to form each of the above layers.
This is accomplished by further adding and feeding into the reaction chamber 201.

Example 1 Layers were formed on an aluminum substrate using the round manufacturing apparatus IIK shown in FIG. 3 under the following conditions.

The formed member thus obtained was charged and exposed to light.
Corona charging was carried out for 0.2 sac at 7,e5[V, and the V light image was immediately irradiated.The light source was a tungsden lamp, and the light intensity of 1.0/ux@set was applied to the transparent I.
Irradiate using an M-type test chart.

Immediately thereafter, a charged toner image (containing toner and carrier) was cascaded over the surface of the component to form a good toner image on the surface of the component.

One toner thus prepared was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. □Even if the number of repetitions is 150,000 II or more, the deterioration of the image does not occur and the image does not deteriorate.

Longevity Example 2 Using the manufacturing equipment shown in Figure 3, the above)-t
III formation was carried out under conditions i).

Other conditions were the same as in Example 1.

The thus obtained one-sugi member was placed in a charging exposure device, and corona charging was applied for 0.2 g at θ5 KV.
Chiriko light image was irradiated. A Tangeston lamp was used as a light source, and a light intensity of 1.0 /ux*see was irradiated using a transmission range test chart.

Immediately after that, ■M-area developer (toner and
By cascading the toner onto the surface of the component, a good toner 11 is deposited on the surface of the component. I'm a comic.

The toner image thus obtained is cleaned with -H rubber grade, and the above image forming and cleaning steps are repeated again. No deterioration of the image was observed even after repeating the process 10υ″−μ.

Example 3 Using the apparatus shown in FIG. 3, the following -Ji-
1-formation was performed in this case.

The other conditions in Example 7 were the same as in Example 1.

The image-forming material obtained in this manner was placed in a photo-exposure and development apparatus, and corona discharge was performed at (-)5KN for 02 exposures to irradiate it with a light amount of 11 liters. A tungsten/lamp was used as the light source, and a transparent type 1st chart was used to irradiate with a light amount of 1,Q/ux-+ec.

Immediately thereafter, by cascading a charged iA1 agent (including toner and carrier) onto the surface of the member, a good toner image with extremely high concentration was obtained on the surface of the member.

The thus obtained toner was cleaned with a -a rubber blade, and then cleaned again using the above-mentioned cleaning method.
kIIIk returned. Repeat count 15b° or more row 9
Example 4 Auxiliary 1-9 Formation of charge injection prevention layer and amorphous layer (I))j
The method is changed as shown in Table 44, and the amorphous fiber 11 (
Example 3 was performed except that during the formation of 1), the pile ratio of silicon urethane and graphite was changed, and the content ratio of silicon atoms and carbon atoms in the second amorphous layer was changed. A forming member was made in exactly the same manner.

In this way, for each wall forming member obtained above, 900, f'H'J1, as described in Example 1. JJtial, a bond that has gone through the cleaning process about 50,000 times - 111#IF
When I did a reconnaissance, I got Nori 11 on Table 5.

, 7/ 7, / l@Table 5 ■, Very good O/Good Δ: Sufficient for practical use ×0 Easy to cause image defects/ / Example 5 Except for changing the thickness of the amorphous layer (seal) prepared a cleft-forming member by the same method as in Example 1. As described in Example 1, the process of making a monk, cleaning a samurai is repeated, and the result of T1 is a samurai.

,' Table 6 Example 6 Method of forming layers other than amorphous 4(1) The hot water forming member was formed in the same manner as in Example 1, except that all the lower plates were changed. It was evaluated using the same method as in Example 1, and good results were obtained.

/ 11 Masa 58-14595306) Example 7 A 1#I forming member was created in the same manner as in Example 1, except that the method of forming layers other than the amorphous layer was changed as shown in the table below. When divalent analysis was carried out using a method similar to Example 1 and flf1, good results were obtained.

,, /” 7” Example 8 Example 1. 2. 3. 4. 6. In step 7, an image forming member was prepared according to the conditions and procedures in each example except that the conditions for forming the amorphous layer (I) were as shown in the table below. When we conducted a similar evaluation,
Good results were obtained.

/″

[Brief explanation of the drawing]

FIGS. 1 and 2 each schematically show a VC structure of a preferred embodiment of the photoconductive member of the present invention, and FIG. It is a typical explanatory view showing an example of the device for manufacturing a member. 100, 200...Photoconductive member 101, 201...Support body 102, 202. 204... Auxiliary layer 104, 2
05...First amorphous, '1l (I) employee
To Canon Co., Ltd.-4-j

Claims (1)

[Claims] The light guide # is used as a support for the member, and the silicon atom is used as a base material.
, nine auxiliary layers made of an amorphous material containing sit elementary atoms as constituent atoms, and a silicon atom matrix,
A charge injection prevention layer made of an amorphous material containing atoms belonging to Group Ⅰ of the Eleventh Table of Contents as constituent atoms, and a charge injection prevention layer made of an amorphous material containing silicon atoms as a matrix and exhibiting photoconductivity. a second amorphous layer provided on the amorphous layer and made of an amorphous material containing silicon atoms and return atoms as constituent atoms; The charge injection prevention layer has a layer thickness t of 305 μm or more and less than 0.3 μm, and the amount C (V) of atoms belonging to group V of the periodic table contained in the charge injection prevention layer is 33 atoms. The direct C(V) is 1111 or more, or the type is 30λ or more and one of the above C(V)
is 30 atomic- or more and 100 atomic
A photoconductive member characterized in that it is less than p.