JPS58147750A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoconductive material suitable for electrophotography, etc., and superior in durability, etc., by successively forming on a substrate, an auxiliary layer, a charge injection preventive layer, first and second amorphous layers, each layer made of an amorphous material consisting mainly of Si. CONSTITUTION:Layers 102, 103, 104, 105 formed on a substrate 101 are made of amorphous material consisting mainly of Si. An auxiliary layer 102 is formed on the substrate 101 and consists of Si, H, and N up to 25 atomic %. On this layer a charge injection preventive layer 103 is formed and consists of Si and an atom of group V of the periodic table, such as As. On this layer 103 a first amorphous photoconductive layer 104, and a second amorphous layer 105 consisting of Si and C are formed in due order, thus forming an objective photoconductive naterial 100.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to electromagnetic waves (sensitive photoconductive Regarding parts.

As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic f-image forming member in the field of f-image forming, or a document reading device, it is highly sensitive and has a photocurrent (I
p)/dark electricity 151 (Id)), has absorption spectrum characteristics that match the spectral characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has the desired dark resistance, and is resistant to the human body during use. Furthermore, in solid-state imaging devices, ls! characteristics such as being able to easily process concerns within a predetermined time are required. Particularly in the case of an electrophotographic image 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 silicon (hereinafter referred to as a-81) is a photoconductive material that has recently attracted attention.
No. 85371s describes its application as an f-image forming member for electrophotography, and Kyokoku Publication No. 2933411 describes its application to a charging conversion/reading device.

Heigo and others, conventional 1-8! A photoconductive member having a photoconductive layer composed of: l!
In terms of stability over time and durability, each individual property has been improved, but when measuring the overall properties, l! The reality is that there is room for improvement.

For example, when applied to electrophotographic image forming members, when trying to achieve high light sensitivity and high dark resistance at the same time, it has often been observed that residual potential remains in conventional traps during use. When a conductive member is used repeatedly for a long period of time, it has many disadvantages such as the accumulation of fatigue due to repeated use and the so-called ghost phenomenon in which residue remains.

In addition, when forming a photoconductive layer using an a-8i material, in order to improve its electrical and photoconductive properties, hydrogen atoms, halogen atoms such as fluorine atoms, chlorine atoms, etc., and electrically conductive Boron atoms, phosphorus atoms, etc. are included in the TIC as constituent atoms in the photoconductive layer to control the type, or other atoms are included in order to improve other properties, but the manner in which these constituent atoms are contained is determined. Depending on the situation, problems may arise in the electrical or photoconductive properties, pressure resistance, durability, etc. of the formed layer.

That is, when used as an f-image forming member for electrophotography, for example, the lifetime of photocarriers generated by photoconduction in the formed photoconductive layer may not be sufficient, or the charge on the support side may not be sufficient in the dark area. Image defects may occur due to insufficient prevention of the injection of the image, or a local discharge breakdown phenomenon commonly referred to as "one white missing on the image transferred to the transfer paper," or, for example, when cleaning There was a paper with 111 image quality defects where it was said that ``feKr white streaks'' were caused by the friction caused by the use of a blade. Furthermore, when used in a humid atmosphere or immediately after being left in a humid atmosphere for a long time, so-called blurring of the image often occurs.

When the layer thickness exceeds 10-odd microns, the layer may lift or peel off from the surface of the support, or the layer may peel off as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. This resulted in problems such as the formation of cracks. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, so it should be solved in terms of stability over time) ( be.

Therefore, while efforts are being made to improve the properties of the a-8i material itself, it is necessary to take measures to solve all of the above-mentioned problems when designing photoconductive members.

The present invention has been made in view of the above points, and has applicability and applicability to A-8I as a photoconductive member used for Vcfe such as an f-image forming member for electrophotography, a solid-state imaging device, and a reading device. As a result of comprehensive research and consideration from this perspective, we have developed an amorphous material that uses silicon atoms as a matrix and contains at least either a hydrogen atom I or a halogen atom head, so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or Halogen-containing hydrogenated amorphous silicon [hereinafter referred to as ra-
st (H,X)J]
A photoconductive member manufactured by specifically designing the layer structure of a photoconductive member having 1.11 as described below not only exhibits extremely superior properties in practical use, but also exhibits superior properties compared to conventional photoconductive members. This is based on the discovery that it is superior in all respects when compared, and that it has particularly excellent properties as a photoconductive member for electrophotography.

The electrical, optical, and photoconductive properties of the present invention are almost always stable regardless of the environment in which it is used, and it has excellent resistance to paper cutting and light stress, and does not deteriorate even after repeated use. The object of the present invention is to provide a photoconductive member that has excellent durability and moisture resistance, and in which no or almost no residual potential is observed.

Another object of the present invention is to have excellent adhesion between a layer provided on a support and the support and between each layer of laminated layers,
It is an object of the present invention to provide a photoconductive member that is dense and stable in terms of structural arrangement and has high layer quality.

Another object of the present invention is that when applied as an image forming member for electrophotography, the charge retention ability during charging treatment for forming a static electricity is sufficiently stable, and the ordinary electron density method can be applied very effectively. Photoconductive member f having excellent electrophotographic properties obtained
: To provide.

Another object of the present invention is to provide a photoconductive member for electrophotography that can easily obtain high-quality images with high density, clear halftones, and high resolution. It is to be.

The photoconductive member of the present invention comprises a support for the photoconductive member, and an amorphous material having silicon atoms as a matrix and containing hydrogen atoms as constituent atoms and nitrogen atoms having a content of up to 25a-membered m1C-. A charge injection prevention IF # made of an amorphous material containing atoms belonging to Group V of the periodic table as a base material, and an auxiliary layer composed of silicon atoms as a base material; a first amorphous layer made of an amorphous material and exhibiting photoconductivity; provided on the skeleton amorphous layer;
It is characterized by having a second amorphous layer made of an amorphous material containing silicon atoms and carbon atoms f as constituent atoms.

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

Shows photoconductive properties, pressure resistance, and environmental characteristics for the casing.

In particular, when applied as a II forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, it is highly sensitive, and it has a high 8N ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and has a high concentration.
The halftones are clear and the resolution is excellent.
Quality images can be stably and repeatedly obtained.

In addition, the photoconductive member of the present invention has an amorphous layer formed on the support, which is strong and has excellent adhesion to the support, and can be used continuously at high speed for a long time. Can be used repeatedly.

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

FIG. 1 is a schematic block diagram schematically shown in a circle for explaining the layer structure of a photoconductive member according to a first embodiment of the present invention.

A photoconductive member 100 shown in FIG. 1 includes, on a support 101 for a photoconductive member, an auxiliary layer 102, a charge injection prevention layer 103, and a first amorphous layer (I) having photoconductivity 10.
4, comprising a second amorphous layer (1) 105 composed of an amorphous material (hereinafter referred to as "g-81,01, J") whose constituent atoms are silicon atoms and carbon atoms, Amorphous layer (1) 105 has a free surface 106.

The auxiliary layer 102 mainly consists of the support 101 and the charge injection prevention layer 1.
It is provided for the purpose of measuring the adhesion between the support 101 and the charge injection prevention +#tOa, and is made of a material described below so as to have affinity with both the support 101 and the charge injection prevention +#tOa.

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

The amorphous layer (1) 104 generates photocarriers in the cough layer 104 upon being irradiated with sensitive light, and the photocarriers are generated in a predetermined direction KM.
Mainly has a function of transporting photocarriers.

The amorphous layer ([) 105 is designed to achieve all of the objectives of the present invention mainly in terms of moisture resistance, continuous repeated usage characteristics, pressure resistance, usage environment characteristics, and durability. : Provided.

The auxiliary layer in the present invention is an amorphous material (hereinafter @- (8iaNt-a)bHt
It is written as -b. However, it is composed of 0°6 (a, 0.65≦b).

The auxiliary layer composed of a-(8i, ri, -a)bHt-b can be formed by a four-discharge method, a sputtering method, an implantation method, an ion grating method,
This can be done using traps such as the electron beam method. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, level of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. The glow discharge method is used because it is relatively easy to control the manufacturing conditions for manufacturing conductive members, and it is easy to introduce nitrogen atoms and hydrogen atoms together with silicon atoms into the auxiliary layer to be manufactured. Alternatively, a sputtering method is preferably employed.

Furthermore, in the present invention, a glow discharge method and a sputtering method may be used together in the same apparatus to form the intermediate layer 102 tube.

To form the auxiliary layer by glow discharge method, Maro-(8
l, Ns-m) bHt-b forming raw material gas is mixed with dilution gas at a predetermined mixing ratio as needed,
The introduced gas is introduced into a deposition chamber for vacuum deposition where the support is installed, and the introduced gas is turned into gas plasma by generating a glow discharge, and a-(SiJt-a)b)I is deposited on the support.
It is sufficient to deposit t-b.

In the present invention, a-(8I @Nr-g) 1iHt
As a raw material gas for forming -b, 81. Almost any gaseous substance containing at least one of N and HO as a constituent atom or a gasified substance that can be gasified can be used. '81
, N, and H, when using a raw material gas with S11 as a constituent atom, for example, a raw material gas with Sl as a constituent atom, a raw material gas with N as a constituent atom, and a raw material gas with H as a constituent atom. Alternatively, the raw material gas containing 5ili constituent atoms and the raw material gas containing N and Hf constituent atoms may be mixed at a desired mixing ratio. It can be used as

Separately, N is added to the raw material gas containing 8i and H as constituent atoms.
The raw material gases t and A, which are 1 constituent atoms, may be used in combination.

In the trap of the present invention, the starting material that can be effectively used to obtain the raw material gas trap component for forming auxiliary 1 is old melon, S-transfer, whose constituent atoms are H and H.

Silane such as 81mto, 814Hto (81tmne
), silicon hydrides containing N or N and H as constituent atoms, such as nitrogen (Ne), ammonia (MHI), hydrazine (Peng NNH,), hydrogen azide (HN, Mention may be made of gaseous or gaseous nitrogen such as ammonium azide (NH4N, ), nitrogen compounds such as nitrides and azides. In addition to these starting materials for forming the auxiliary layer, 1 is of course also effective as a raw material gas for introducing H.

To form the auxiliary layer by sputtering method, monocrystalline or polycrystalline S & Quahar or 81sN*v
) In addition to x-hearth, 8i and N4 may be sputtered in various gas atmospheres using a wafer as a target.

For example, if you use a drawn wafer as a target,
Source gas for introducing N and H, e.g.
Hm t's may be diluted with a diluent gas as necessary, introduced into a deposition chamber for sputtering, and sputtered by forming a gas plasma of these gases.

Alternatively, sputtering can be performed in a gas atmosphere containing at least 4H atoms by using separate targets from IN4 or by using a single target formed by mixing 8i and 86N. It is accomplished by

As a raw material gas for introducing N or H, the starting material gas for forming the auxiliary layer shown in the example of the four-discharge mentioned above can also be used as an effective gas in the case of sputtering. .

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 appetizer gas, an example is He.

Suitable examples include Ne, Mr, and the like.

""'("aNl-a)bH constituting the auxiliary layer of the present invention
The function of the auxiliary layer is to strengthen the adhesion between the support and the charge injection prevention layer, and also to make the electrical contact between them uniform. The manufacturing conditions are strictly selected and carefully formed so that the desired properties are imparted to the desired properties.

a-(81°Nx-) having characteristics suitable for the purpose of the present invention
a) An important element in the production conditions for producing bHl-b is the temperature of the support during production.

That is, the surface of the support K a -(81BN@-@)
1) When forming an auxiliary layer consisting of Ht-is, the temperature of the support during layer formation is an important factor that influences the structure and properties of the formed layer. The temperature of the support at the time of layer formation is strictly controlled so that a-(84＠小、-a)bHt-b having the following properties can be produced 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, it is preferably #1too at 50℃ to 350℃.
℃~250℃ is desirable. To form the auxiliary layer, charge injection prevention layer, charge injection prevention layer,
Delicate control of the composition ratio of atoms constituting each layer and control of layer thickness allows continuous formation of an amorphous layer and even other layers formed on the amorphous layer if necessary. The glow discharge method and sputtering method are advantageous because they are relatively easy compared to other methods, but when forming the auxiliary layer using these layer formation methods, the above-mentioned The support temperature is cited as an important factor.

In order to achieve the object of the present invention, a-
(8ia Arashi t-a) bHt-b is normally formed as a discharge power condition of 1 to soo
w, preferably 2 to 100W. The gas pressure in the deposition chamber is usually 0.0 when layer formation is performed by glow discharge.
1~1sT6rr, preferably 0.1~&5 Torr
When the NI layer is formed by sputtering, it is generally desirable to set the temperature to 1 G-'' to 5×10-” Torr, preferably 5×1 G-” to 3×1 G-” Torr.

The group of nitrogen atoms (N) and hydrogen atoms (H) contained in the auxiliary layer in the photoconductive member of the present invention is similar to the manufacturing conditions of the auxiliary layer, so that the desired characteristics for achieving the object of the present invention can be obtained. This is an important factor in the formation of an auxiliary layer.

The amount C(11) of nitrogen atoms (N) contained in the auxiliary layer in the present invention is usually within the above-mentioned range, but a
If it is expressed as tomic-, it is preferable that I X 10-”≦
C(w) (z s , preferably 1≦C(N)
(2B.

Optimally, it is desirable that 10≦C(*)<25.

Also, hydrogen atoms (in terms of the amount of river, 2 to S S
mtnmic% eoptimally 5-30 atomic-
It is desirable that this is done. Turtle-(8i aNi-a)
When expressed as a and b in bHt-bK, the value of Maro is preferably 0.6<1≦0. ! 99'! 9. More preferably 70 strokes a≦99. Optimally 0.6 (11≦
0.9. As for the value of b.

Preferably 0.65≦b≦0.98, more preferably 0.
It is desirable that 7≦b≦0.95.

The numerical range of the layer thickness of the auxiliary layer in #41c of the present invention is appropriately determined as desired so as to effectively achieve the object of the present invention.

The thickness of the auxiliary layer to effectively achieve the object of the present invention is usually 30f~2μ, and the preferred thickness is 40A'~1μ.
．． 5μ, optimal (is preferably 5of to 1.5μ).

The charge injection prevention layer constituting the photoconductive member of the present invention has a silicon atom (H) as a matrix, and preferably contains hydrogen atoms (H) or atoms belonging to Group V of the periodic table (Group II atoms). Amorphous material (hereinafter referred to as "a-8i (V, H, x) J
t'fef) te structure 111. The content of the group V atoms C(v) in the layer thickness and the content C(v) of the group V atoms in the layer are appropriately determined as desired so that the objects of the present invention are effectively achieved.

In the present invention, the layer thickness t of the charge injection prevention layer is preferably 0.3 to 5 μm, preferably 0.5 to 2 μm, and the content of Group V elements is preferably 0.3 to 5 μm. C(v) is preferably l1txxot~IX1G"
Atomic ppm, preferably 5X10
It is preferable that the amount is 1 to 10' atomic ppm.

In the present invention, P (phosphorus) is used as an atom belonging to Group V of the periodic table contained in the charge injection prevention layer.
, As (arsenic), sb (antimony), Bi (bismuth), etc., and particularly preferably used are P, As
It is.

In the present invention, specific examples of the halogen atom (X) contained in the charge injection prevention layer if necessary include fluorine, chlorine, bromine, and iodine, particularly fluorine and salt
can be cited as a suitable book.

a-81 (VsHeX) ・For the formation of the charge injection prevention layer, as in the case of forming the auxiliary layer, a discharge phenomenon such as glow discharge method, sputtering method, or ion blating method is used. A vacuum deposition method is employed. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, the level of equipment capital investment, and the desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing conductive members, and in addition to silicon atoms, group V atoms, and if necessary, hydrogen atoms (H) and halogen atoms (X) are created in the charge injection prevention layer. The glow discharge method or the sputtering method is preferably employed because of the advantage that it can be easily introduced.

Furthermore, in the present invention, the charge injection prevention layer may be formed by using both the glow discharge method and the sputtering method in the same apparatus system.

For example, by the glow discharge method, a-8i (■).

K to form a charge injection prevention layer composed of
Basically, silicon atoms (8) are supplied together with a raw material gas for false supply, a raw material gas for introducing group (III) atoms that can supply group V atoms, and hydrogen atoms (as necessary).
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 in the corpse deposition chamber, which has been installed at a predetermined position in advance, of a given support, which is the provision of an auxiliary layer.
1. It is sufficient to form a layer consisting of m-8i (V, H, 81 in a mixed gas atmosphere based on
When sputtering a target composed of
Hydrogen atoms (H
) or/and halogen atoms (,
.

In the present invention, the following starting materials are used to form a charge injection prevention layer using tCJ and are used as raw material gases.
#-3゜The starting material that becomes the raw material gas for supplying 8i is 8i.
1B6, 81; 1%, 8! 3Ha, 81. H
, e, etc., or silicon hydride (silanes) which can be gasified are mentioned as those which can be effectively used. In particular,
8i in terms of ease of handling layer creation work, good separate supply efficiency, etc.
Preferred examples include H4,81 and HI.

Using these starting materials, KH as well as 8-length can be introduced into the auxiliary layer formed by appropriately selecting the layer forming conditions.

In addition to the above-mentioned silicon hydride, effective starting materials that can be used as raw material gas for supplying gas include silicon compounds containing halogen atoms (X), waste cocoons, silane trout conductors substituted with /%llllgen atoms, For example, 81F4, 8iJ@,
/% Q silicon ions such as 8iC4, 81Br4, etc. can be mentioned as preferable ones, and furthermore, 81%F1
．． 81%11, 81%c4, 81Hc4, 8i
H, B r@.

Halogen-substituted silicon hydrides such as 8 i HB r@, etc., and halides that have hydrogen atoms as one of their constituents in a gaseous state or can be gasified, can also be used for supplying 8e for forming an effective charge injection prevention layer. It can be mentioned as a starting material.

When these silicon compounds containing halogen atoms (X) are used, as described above, WCXt can be introduced together with 81 into the charge injection prevention layer formed by appropriately selecting the layer forming conditions.

Among the above-mentioned starting materials, halogenated silicon compounds containing hydrogen atoms contain halogen atoms (X) in the layer when forming the auxiliary layer.
Hydrogen atoms, which are extremely effective for controlling electrical or charging characteristics, are also introduced at the same time as the introduction of halogen/atom (X). .

In addition to the above-mentioned materials, effective starting materials that serve as the raw material gas for introducing halogen atoms (X) used when forming the auxiliary layer in the present invention include, for example, fluorine, chlorine,
Bromine, halogen gas, BrF, CjF,
CLIFF, BrFl, BrFl, IFF.

Intergen compounds HF such as IFy, ICt, IBr, etc.

Examples include hydrogen halides such as HCA, HBr, and HI.

Kt that structurally introduces trap group III atoms into the charge injection prevention layer
i. During layer formation, the starting material for introducing Group V atoms may be introduced in a gaseous state into the deposition chamber together with other starting materials for forming the charge injection prevention layer. As the starting material for introducing such group V atoms, it is desirable to use a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions.

As a starting material for such a VS* particle introduction, specifically, for the introduction of a phosphorus atom, Pus, Pt)I4, etc.O phosphorus hydride, PH4I, PF,, PF,, PO
2, PO2, PBr.

Examples include halogen gases such as PBr and PIE.

In addition, AsHl, AsFl, k*c4,
AsBr1, AsFg, 5bii, .

8bF1 , 8bFs, , 8bCJ, , 5bCJ, ,
, BiH, B1C4, B1Br1, etc. can also be mentioned as effective starting materials for introducing Group V atoms.

In the present invention, the group (III) atoms contained in the charge injection preventing layer in order to provide charge injection preventing properties are contained in the charge injection preventing layer in a plane substantially parallel to the 1-thickness direction (the surface of the support). In the plane (parallel to the plane) and in the layer thickness direction, the distribution is substantially uniform.

Furthermore, when forming the charge injection prevention layer by sputtering, S! When performing sputtering, the raw material gas for introducing group V atoms is sputtered together with the raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. It is sufficient to introduce it into the vacuum deposition chamber where the process is carried out.

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 the VS* particles flowing into the deposition chamber. , the temperature of the support, the pressure inside the deposition chamber, etc. can be arbitrarily controlled.

In the present invention, as the . . . -gen atom (X) contained in the charge injection prevention layer if necessary, the same atoms as those described in the description of the auxiliary layer can be mentioned.

In the present invention, the gases used when forming the charge injection prevention layer by the glow discharge method or the sputtering method include so-called rare gases, such as He, Ne, and Ar.
etc. can be mentioned as suitable ones.

In the present invention, a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion grating method is used to form the first amorphous layer (1) composed of m-8i (l(, For example, a-st(H,X
) to form an amorphous layer consisting of hydrogen atoms (H) and/or halogen atoms ( X) A raw material gas for introduction is introduced into a deposition chamber whose interior can be made to have a reduced pressure, and a glow discharge is generated in the deposition chamber to generate a glow discharge that has already been formed on a predetermined support surface that has been placed in a predetermined position. K m −8i (H
, X) may be formed. In addition, when forming by a sputtering method, for example, when sputtering a target composed of 8 gases in an atmosphere of an inert gas such as R, He, etc. or a mixed gas such as these gas pipes, hydrogen atoms are (H) It's okay to introduce the gas for introducing I/Rogen atoms (X) into the sputtering chamber HIm.

In the present invention, as the halogen gas (X) contained in the amorphous Nlj (1) if necessary, the same ones as mentioned in the case of the auxiliary layer can be mentioned.

In the present invention, the raw material gases for supplying St used to form the amorphous layer (1) include 8iH4, 8ilH,
, 8i1%, 814H16, and other gaseous or gasifiable silicon hydrides (silanes) can be effectively used, and in particular, they are easy to handle in layer creation work, have good separate supply efficiency, etc. In this respect, Betsu Ha and 81 Years Hs are preferred.

In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer 0), as in the case of the auxiliary layer, such as halogen gas, halides, interhalogen compounds,
Preferred examples include gaseous or gasifiable halogen compounds such as halogen-substituted silane derivatives.

Furthermore, silicon atoms (Sl) and halogen atoms (X
) and which are in a gaseous state or can be gasified and contain halogen atoms can also be mentioned as effective in the present invention.

In the present invention, the amorphous layer (1) K contains a substance that controls sound conduction characteristics, so that the conduction characteristics of the cough layer O can be arbitrarily controlled as desired.

Examples of such substances include rust and impurities referred to in the semiconductor field. In the present invention, the a-81 (H, ) K
On the other hand, Fil impurities that give P-type conductivity characteristics, specifically, atoms belonging to Group 2 of the periodic table (group 3 atoms), such as B (1#I element).

Aj (aluminum), Ga (gallium), Ifl (indium).

TA (thallium) and the like are particularly preferably used at 8%0m.

In the present invention, the content of the substance that controls the conduction properties contained in the amorphous layer 0) depends on the conduction properties required for the amorphous layer (S) or directly on the layer (iris). It can be selected as appropriate based on the organic relationship, such as the characteristics of other layers provided in contact with the layer and the relationship with the characteristics at the contact interface with the layer.

In the present invention, the content of the substance that controls conduction properties contained in the amorphous layer 0) is usually 0.0
01-1000 atomic ppm, preferably 0.
0 S to 500 atomic ppm, optimally 0.
It is desirable that the content be 1 to 200 atoms ppm.

In order to structurally introduce a substance that controls conduction properties, such as a group 1 atom, into an amorphous layer, a starting material for introducing a group 1 atom is introduced in a gaseous state into a deposition chamber during layer formation. The starting materials for introducing Group 1 atoms, which can be introduced together with other starting materials for forming an amorphous layer, are gaseous or at least layer-forming at room temperature and pressure. It is desirable to use a material that can be easily gasified under the formation conditions. As a starting material for introducing such a Group 1 atom, specifically for introducing a boron atom, BIHI * BIHI6
m BIHI # BsHn * BsHto +
Bean *Boron hydride such as B@H14, B11 *
Examples include boron halides such as BO2e BBrm. In addition, AtC4゜GaC4, Ga(CHI)1,
InC4, TAC4, etc. can also be mentioned.

In the present invention, hydrogen atoms (
The amount of H) or the amount of halide (X) or the sum of the amounts of hydrogen atoms and halogen atoms (X) (H + X) is usually 1 to 40 atomicL, preferably 5 to 30 atomicL.
It is preferable to use mic$. 1 To control the amount of hydrogen atoms (X) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer (1), for example, the support temperature or/and the amount of hydrogen atoms (X) Alternatively, in order to contain halogen atoms (X) t-, the amount of the starting material used as a trap introduced into the deposition system, the discharge force, etc. may be controlled.6 In the present invention, the amorphous layer (1) The diluent gas used when forming K11l! by the glow discharge method, or the sputtering gas used when forming by the sputtering method, is a so-called mineral gas, such as He, Ne, etc.
, Ar, etc. can be cited as suitable examples.

In the present invention, the thickness of the amorphous layer is determined as appropriate depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 100 μm, preferably It is desirable that tL< is 1 to 80μ, most preferably 2 to 50μ.

In the photoconductive member of the present invention, the first amorphous 1 m (
1) The second amorphous layer (i) provided thereon is made of an amorphous material (a-81x
Cs-2, where O < Since it has the following constituent elements, chemical stability is sufficiently ensured at the laminated interface.

a-stXct-, the second amorphous layer (厘)
Formation is performed by line sputtering method, ion implantation method, ion grating method, electron beam method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, equipment capital investment, manufacturing scale, and the photoconductive member to be manufactured (desired characteristics). It is relatively easy to control the manufacturing conditions for manufacturing photoconductive members, and the second amorphous layer is made of one carbon atom along with a silicon atom (sputtering is used because it can be easily introduced into the second amorphous layer). The ring method, the electron beam method, and the ion brating method are preferably employed.

To form the second amorphous layer (1) by the sputtering method, a monocrystalline or polycrystalline Sl kneebar and a carbon
It would be refreshing to perform sputtering using a Ueno-t target containing a mixture of Wa-1 or old and C in various gas atmospheres.

For example, when using 1 ueno and C waeno as targets, a sputtering gas such as He, N@, Ar, etc. is introduced into a deposition chamber for sputtering to form a gas gufsma. What is necessary is to sputter the above-mentioned puller and C-Queno.

Another method is to use a single target tt mixed with C and C, by introducing a sputtering gas into the apparatus system, and performing sputtering in the gas atmosphere. When using the electron beam method, single-crystal or polycrystalline O high-purity silicon and high-purity graphite are placed in two evaporation boats, and each is independently co-deposited using an electron beam trap, or the same evaporation boat is used. The content ratio of silicon and carbon contained in the second amorphous layer is the same as that of the former. In the latter case, it is controlled by changing the electron beam acceleration voltage with respect to silicon/graphite, and in the latter case, it is controlled by predetermining the mixing amount of silicon and graphite. When using the ion grating method, various gas pipes are introduced into the deposition tank, and a high-frequency electric field is applied to coils placed around the tank in advance to create a grating, and then the electron beam method is used. What is necessary is to vapor-deposit hydrogen and C.

In the present invention, the second amorphous layer (1) is carefully formed so that its required properties are imparted as desired.

In other words, substances whose constituent atoms are sI, C, have a structure ranging from crystalline to amorphous depending on the conditions of creation.
In terms of electrical properties, it exhibits properties ranging from conductivity to semiconductivity to insulating properties, and properties ranging from photoconductive properties to non-photoconductive properties. In order to form 1-8izCt-x containing the desired characteristics aimed at the purpose, the preparation conditions are strictly selected according to the desired purpose.

For example, to provide a second amorphous layer (layer) with the main purpose of improving pressure resistance, m-811 ((4-1 is an amorphous layer with remarkable electrically insulating behavior in the usage environment). Created as a material.

In addition, if a second amorphous layer is provided for the main purpose of improving the characteristics of continuous repeated use or the characteristics of the usage environment,
The degree of electrical insulation is relaxed to some extent, and a-8+1 (4-1) is produced as an amorphous material having a certain degree of sensitivity to irradiated light.

Table of first amorphous layer (I) TICa-8i
, 1Ct -1, the support temperature during layer formation is an important factor that influences the structure and properties of the formed layer, and the present invention In this case, it is desirable to strictly control the temperature of the support during layer formation so that a -81zc@-X having the desired properties can be formed as desired.

The temperature of the support when forming the second amorphous layer (seal) in order to effectively achieve the purpose of the present invention is the method for forming the second amorphous layer (seal). The second amorphous layer (1) is formed by selecting an optimal range accordingly.
The preferred trap temperature is preferably 20-300°C, optimally 20-250°C.

In forming the second amorphous layer (1), delicate control of the composition ratio of atoms constituting the layer and control of the layer thickness are relatively easy compared to other methods. It is advantageous to adopt a sputtering method or an electron beam method, but when forming the second amorphous layer (1) using these layer forming methods, the temperature of the layer formation as well as the support temperature described above must be adjusted. The actual discharge power can be cited as one of the important factors that influences the characteristics of the R-81XCI-x.

a having the characteristics for achieving the object of the present invention;
-811CI-〇 is suitably 50W~tsow,
@It is desirable that the power is suitably 80W to 150W.

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second amorphous layer (■) include the values in the above ranges, but these layer creation factors are It is desirable that the optimum value of m-81101-1 for the desired characteristic be determined, rather than being determined independently and separately.

The amount of carbon atoms contained in the second amorphous layer (layer) in the photoconductive member of the present invention achieves the objective of the present invention as well as the second amorphous layer (1) O production conditions. This is an important factor in forming a layer that provides the desired properties.

The amount of carbon atoms contained in the second amorphous layer (1) in the present invention is usually lXl0 to 90 atoms, preferably 1 to 80 atoms, based on the sum of silicon atoms and carbon atoms. -1 Optimally 10-75 atoms
It is desirable that it be le-.

In other words, if we display X in a-81101-X above,
is usually 0.1 to 0.99999, preferably 0.2 to o
, 99, optimally between 0.25 and 0.9.

The numerical range of the layer thickness of the second amorphous layer (m) in the present invention is appropriately determined according to the desired purpose so as to effectively achieve the purpose of the present invention.

In addition, the layer thickness of the second amorphous layer (layer) depends on the amount of carbon atoms contained in the core layer (layer) and the layer thickness of the first amorphous layer (1). However, it is necessary to appropriately determine the desired characteristics based on organic relationships depending on the characteristics required for each layer region.

In addition, it is also important to consider economic efficiency, which takes into account productivity and mass production.

The layer thickness of the second amorphous layer (seal) in the present invention is as follows:
Usually 0.003-30μ, preferably 0.004-20μ
The optimum thickness is preferably 0.005 to 10μ.

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

kA, Cr, Mo, Au, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pd, and alloys thereof.

Polyester is used as an electrically insulating support.

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

PO9tJ [films or sheets of synthetic resins such as vinylidene chloride, polystyrene, polyamide, and glass;

Setumik, paper, etc. are usually used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface 11.

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

AA, Cr, Mo, Au, Ir, Nb, T
a, V, Ti, Pt, Pd.

Int(%, 8n01 I ITO(In2O3+
Conductivity is imparted by providing a thin film consisting of NiCr, AA, Ag, etc., or if it is a synthetic resin film such as a polyester film.
Pb, Zn, Ni, Au.

Cr, Mo, Ir, Nb, Ta, V, TI
, thin films of metals such as Pt are deposited by vacuum evaporation, electron beam evaporation,
Conductivity is imparted to the surface by sputtering or the like, or by laminating the surface with the metal. The shape of the support is cylindrical.

The photoconductive member Z shown in FIG.
If oo is used as a law forming member for electrophotography, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying. The thickness of the support is appropriately determined so as to form a photoconductive member with the desired thickness, but if flexibility is required as a photoconductive member, the thickness of the support may be adequately determined. It is possible to make it as thin as possible within the specified range. In such cases, in manufacturing and handling of the support,
In consideration of mechanical strength, etc., the thickness is usually 10μ or more.

FIG. 2 shows another preferred embodiment of the photoconductive member of the present invention! 1
An example layer configuration is shown.

The photoconductive member 200 shown in FIG. 2 is different from the photoconductive member 100 shown in FIG. 204.

That is, the photoconductive member 200 includes a lower auxiliary layer 202, a charge injection prevention layer 203, and a lower auxiliary layer 202, which are laminated in order on a support 201, a balance sheet 111, and a charge injection prevention layer 203. Upper auxiliary layer 204. The first amorphous layer (1) zos and the second amorphous layer (1) 20g are provided, and the amorphous layer (w) 206 is a free table 11j2G?
The number with The upper part, the auxiliary layer 204ti, the charge injection prevention layer 203, and the amorphous layer (1) strengthen the adhesion between GOS and 0, and make the electrical contact uniform in both layers. , charge injection prevention layer 2 (KIE on I31o
Prevents charge injection by providing K #2＠＄61
Make m-quality strong.

The lower auxiliary layer 202 and the upper sum layer Z4 shown in FIG. In the case of 1O2, using the N-hating O base crystal material, the layer is formed by similar layer formation procedures and conditions so as to provide similar properties. Charge injection prevention Jl120B and amorphous layer (1)! The charge injection prevention layer 103, the amorphous layer (1) 104, and the amorphous layer (1) shown in FIG.
It has the same properties and functions as 10B, and is formed by the same layering and conditions as in the case of 1s.

Next, a method of manufacturing a photoconductive member produced by the vacuum deposition apparatus shown in FIG. 3 will be described.

In each of the gas cylinders 302 to 306 in the figure, the gases used to form the respective layers of the present invention are closely coupled. 8 Qianpeng Gas (#degreetlJt19!, hereafter F8i
It is abbreviated as H&/He. ), but the cylinder -3Qs has He
P gas diluted with (purity! 9.999-1 or less P
It is abbreviated as Hs/He. ) is in the cylinder 304, 84F gas diluted with He (purity 99.99, hereafter 8!F4/
It is abbreviated as He. ) in the cylinder 305: TiN-gas (pure [119,999%), but in the cylinder 306 trap the Ar gas (
purity! 9.999%) respectively. It goes without saying that the type of gas filled in a cylinder such as this may be changed as appropriate depending on the type of layer to be formed.

Each valve 312 to 32 of the gas cylinders 302 to 306 is used to flow these gases into the reaction chamber 3()1.

Make sure that the leak valve 335 is closed, and also close the inlet valves 312 to SX and the outlet valves 317 to 32.
1. Make sure that the auxiliary valve 332 is open, and then open the main valve 334 to exhaust the reaction chamber 301 and gas piping.The vacuum gauge 336 reads approximately 5X1.
When the temperature reaches 0-'torr K, the auxiliary valve 332 and the outflow valves 317 to 321 are closed.

Thereafter, a desired gas is introduced into the reaction chamber 301 by operating the valve of the gas pipe connected to the gas cylinder to be introduced into the reaction chamber 301 as prescribed.

Next, an outline of an example of producing a photoconductive member having the configuration shown in FIG. 1 will be described.

81H4/He gas from gas cylinder 302, Nho gas from gas cylinder 305, valves 321 and 325, respectively.
After opening the outlet pressure gauges 327 and 330, the pressures are 1#, respectively.
Adjust Kf14 so that it becomes /-, then turn on the flow, inlet valve 312.
, 315 are gradually opened to allow flow into the mass 70-controllers 307, 310, respectively. Subsequently, the outflow pulp 317, 320 and the auxiliary valve 332 are opened in sequence to allow the respective gases to flow into the warping chamber 301. At this time, the openings of the outflow valves 317 and 320 are adjusted so that the ratio of the 81H,/He gas flow rate to the Peng gas flow rate becomes the desired value, and the openings of the outflow valves 317 and 320 are adjusted until the pressure inside the reaction chamber 301 reaches the desired value. Adjust the opening of the main pulp 334 while checking the reading on the vacuum gauge 336.

After confirming that the temperature of the support 337 is set to a temperature in the range of 50 to 400 degrees Celsius by the heater 338, the power source 340 is set to the desired power to cause glow inside the reaction chamber 301. Create a discharge and hold this gummy for a desired time.
The 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, the power supply 340 is turned off 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 chamber 301 is discharged to the outside of the reaction chamber 301. to the specified degree of vacuum.

After that, the old Ha/He gas is supplied from the gas cylinder 302 and the PHs/He gas is supplied from the gas cylinder 303 through the valve 8.
2! , 32m 1-open outlet pressure gauge 327,
328 pressure by 1#/dK, respectively, and the inflow valve 312
゜51st each gradually opened, 1 step 0 controller 3
07 and 308, respectively. Subsequently, the outflow pulps 317, 318 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 3ot.

At this time, the outflow pulp is 317°3 so that the ratio of the other H4/H gas flow rate and the PH,/He gas flow rate becomes the desired value.
18 and also adjust the opening of the main valve 334' while checking the reading on the vacuum gauge 336 so that the pressure inside the reaction chamber 301 reaches the desired value. After confirming that the temperature of the support 337 is set to a temperature in the range of 50 to 400° C. by the heating heater 338, the power source 340 is set to the desired power to generate a gummy discharge in the reaction chamber 301. A glow discharge is generated and maintained for a predetermined period of time to form a charge injection prevention layer of a desired layer μ on the auxiliary layer.

Formation of the first amorphous layer (1) is performed, for example, in the cylinder 302.
This can be carried out by using the 8iH4/He gas filled in the 8iH4/He gas and following the same procedure as in the case of the auxiliary layer and the charge injection prevention layer described above.

In addition to 8iH4/He gas, especially 811H
4/l (・gas is effective for improving the layer formation rate.

10. Forming the second amorphous layer (1) on the amorphous layer (1) (is performed, for example, as follows. First, the shutter 34
Open 2. All gas supply valves are once closed, and the reaction chamber 301 is evacuated by fully opening the main pulp 334.

On the electrode 341 to which high-voltage power is applied, a high-purity silicon wafer 342-1 and a high-purity underwear 30 are placed in advance.
6, human gas is introduced into the reaction chamber 301, and the main pulp 334 is adjusted so that the internal pressure of the reaction chamber 301 becomes o, os to ITorr. By turning on the high voltage power supply 340 and sputtering the target, a second amorphous layer (1) is formed on the first amorphous layer (10).

When the auxiliary layer, the charge injection prevention layer, and the first amorphous layer (r) contain hydrogen atoms (X), for example, Pull F4/
This is accomplished by further adding H@ and feeding it into the warping chamber 361.

,-11 Example 1 A layer was formed on an aluminum substrate under the following conditions using the round manufacturing apparatus shown in FIG.

The image forming member thus obtained was placed in a charging, exposing and developing device, corona charging was performed at 95 kV for 0.2 sec, and a light image was immediately irradiated. 1. Using a tungsten lamp. The light intensity of OLux-@ec was irradiated using a transmission type test chart.

Immediately thereafter, a good toner 11iii 11 was obtained on the surface of the member by cascading a Φ-charged present agent (including toner and carrier) over the surface of the member.

The thus obtained toner @ was once cleaned with a rubber blade, and the above image forming and cleaning process was repeated again. No deterioration of the image was observed even after repeating over 150,000 times.

ξI- Example 2 A layer was formed on an At substrate using the manufacturing apparatus shown in FIG. 3 under the following conditions.

Other conditions were the same as in Example 1.

The image forming member thus obtained was placed in a charging, exposure and developing device, corona charging was performed at 5 kV for 0.2 sec, and a light image was immediately irradiated. A tungsten lamp was used as a light source, and a light intensity of 1.0 Aux-sec was irradiated using a transmission type test chart.

Immediately thereafter, a chargeable developer (containing toner and carrier) was cascaded over the surface of the member to obtain a good toner 1 m image on the surface of the member.

The thus obtained toner image tube was once cleaned with a rubber blade, and the above image forming and cleaning steps were repeated again. No deterioration in image quality was observed after repeating over 100,000 times.

Example 3 Layers were formed on 44 substrates under the following conditions using the nine apparatus shown in FIG.

Other conditions were the same as in Example 1.

The scratch-forming member obtained through the process was placed in a charging, exposure and developing device, corona discharge was performed for 2 seconds at 95 kV, and a light amount was immediately irradiated. A tungsten rung was used as the light source.
A light intensity of 1 G 4ux-set was irradiated using a transmission type test chart.

Immediately thereafter, a Φ-charged developer (containing toner and carrier) was cascaded over the surface of the member to obtain an extremely good image on the surface of the member.

The toner image thus obtained was once cleaned with a Go grade, and the above-described image forming and cleaning steps were repeated again. No deterioration of Ryotsu was observed even after repeating the paper more than 150,000 times.
/ Example 4 When forming the amorphous layer (1), the area ratio of the silicon wafer and graphite was changed to adjust the content ratio of silicon atoms and carbon atoms in the second amorphous layer (seal). An image forming member was produced in the same manner as in Example 1 except for the following changes. For the nine image-forming members thus obtained, Example I
Image forming, developing, and cleaning processes as mentioned above are about 5
After repeating the paper 10,000 times, a 111-value test was performed, and the results shown in Table 4 were obtained.

/' / Example 5 A trench-forming member was created in exactly the same manner as in Example 1, except that the thickness of the amorphous layer was changed. The steps of image formation, development, and cleaning as described in Example 1 were repeated to obtain the following results = Table 5/2, /' Example 6 Method of forming layers other than amorphous layer (I) An image forming member was prepared in the same manner as in Example 1, except for changing as shown in the table below.
When evaluation was performed in the same manner as in Example 1, good results were obtained.

Example F An image forming member was prepared in the same manner as in Example 1, except that the method for forming layers other than the amorphous layer (1) was changed as shown in the table below.
When evaluation was performed in the same manner as in Example 1, good results were obtained.

Example 8 Example 1. 2. 3. 6. In step 7, an image forming member was prepared according to the conditions and procedures in each example except that the amorphous layer 0) was formed under the conditions shown in the table below.
When the same evaluation as in each example was performed, good results were obtained.

- 咄 f station also /′

[Brief explanation of the drawing]

The first factor and FIG. 2 are nine schematic layer configuration diagrams each schematically showing the layer structure of a preferred embodiment of the photoconductive member of the present invention.
FIG. 3 is a schematic explanatory diagram showing an example of an apparatus for manufacturing a photoconductive member of the present invention. 100, 200...Photoconductive member 101, 201...Support 102, 202, 204...Auxiliary layer 104, 2
05...10 Amorphous layer (1) 105, 206...
・Second amorphous layer (layer) 108, 207--Free surface applicant Canon Co., Ltd.

Claims (1)

[Claims] a support for a photoconductive member; an auxiliary layer made of an amorphous material based on silicon atoms and containing up to 25 atoms of nitrogen atoms and hydrogen atoms as constituent atoms; A charge injection prevention layer made of an amorphous material containing atoms belonging to Group V of the periodic table as constituent atoms, and a first layer made of an amorphous material having a silicon atomic tube matrix and exhibiting photoconductivity. and a second amorphous layer made of an amorphous material containing silicon atoms and carbon atoms as constituent atoms on the second amorphous layer. A photoconductive member.