JPH0410627B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to light (here, light in a broad sense, including ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, etc.)
It relates to photoconductive members sensitive to electromagnetic waves such as. As a photoconductive material for forming a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device, it is highly sensitive,
It must have absorption spectrum characteristics that match the spectrum characteristics of the electromagnetic waves to be irradiated with a high signal-to-noise ratio [photocurrent (Ip)/dark current (Id)], it must have fast photoresponsiveness, it must have the desired dark resistance value, and when in use Solid-state imaging devices are required to have characteristics such as being non-polluting to the human body, and being able to easily process afterimages within a predetermined time.
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 these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention. As a photographic image forming member, application to a photoelectric conversion reader is described in DE 2933411. However, conventional photoconductive members having photoconductive layers composed of a-Si have poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as use environment characteristics. In terms of stability, stability over time, and durability, each individual property has been improved, but the reality is that there is still room for further improvement in terms of overall property improvement. be. For example, when used as an electrophotographic image forming member, there may be insufficient prevention of charge injection from the support side in dark areas, there may be problems with pressure resistance or durability against repeated and continuous use, or there may be problems with transfer. For example, there may be image defects commonly called "white spots" on images transferred to paper, which are thought to be caused by local discharge destruction phenomena, or, for example, when a blade is used for cleaning, there may be defects caused by the rubbing of the blade. A so-called image defect called "white stripe" sometimes occurred. 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. Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or cracks may develop as the time passes for the layer to stand in the air after being removed from the vacuum deposition chamber for layer formation. It was a victory because it brought about phenomena such as this. This phenomenon often occurs especially when the support is a drum-shaped support commonly used in the field of electrophotography, and there are points that can be solved in terms of stability over time. . Therefore, while efforts are being made to improve the properties of the a-Si 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 includes a
-As a result of intensive research and study on Si from the viewpoint of its applicability as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc., we found that silicon atoms an amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), so-called hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as "hydrogenated amorphous silicon"] "a-Si(H,X)" is used as a generic notation for The photoconductive material produced by this method not only exhibits extremely excellent properties in practical use, but also surpasses conventional photoconductive materials in all respects, and is particularly effective as a photoconductive material for electrophotography. This is based on the discovery that it has excellent properties. The main object of the present invention is to provide a photoconductive member that does not deteriorate even after repeated use, has excellent durability, and also has excellent pressure resistance. Another object of the present invention is to provide excellent adhesion between a layer provided on a support and the support and between each laminated layer, to provide a dense and stable structural arrangement, and to provide layer quality. It is an object of the present invention to provide a photoconductive member with high quality. Another object of the present invention is that when applied as an electrophotographic image forming member, it has sufficient charge retention ability during charging processing for electrostatic image formation, and that ordinary electrophotographic methods can be applied extremely effectively. An object of the present invention is to provide a photoconductive member having excellent electrophotographic properties. The photoconductive member of the present invention includes a support for the photoconductive member, and an auxiliary layer made of an amorphous material having silicon atoms as a matrix, halogen atoms as constituent atoms, and less than 30 atomic percent of nitrogen atoms. , a charge injection prevention layer with a layer thickness of 0.3 to 5μ, which is made of an amorphous material whose base material is silicon atoms and which contains atoms belonging to group of the periodic table as constituent atoms, and an amorphous material whose base material is silicon atoms. It is characterized by having an amorphous layer that is made of a solid material and exhibits photoconductivity. The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the above-mentioned problems, and exhibits extremely excellent durability, pressure resistance, and use environment characteristics. In particular, when applied as an electrophotographic image forming member, its electrical properties are stable, it has excellent light fatigue resistance and repeated use characteristics, and high quality images can be stably and repeatedly produced. 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 continuously used 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 configuration diagram schematically shown to explain the layer configuration of a photoconductive member according to a first embodiment of the present invention. The photoconductive member 100 shown in FIG. 1 is made of an amorphous material that uses silicon atoms as a matrix and contains less than 30 atomic percent of nitrogen atoms and halogen atoms as constituent atoms, on a support 101 for use as a photoconductive member. auxiliary layer 102 , a charge injection prevention layer 103 , and an amorphous layer 104 having photoconductivity. The auxiliary layer 102 is provided mainly for the purpose of measuring the adhesion between the support 101 and the charge injection prevention layer 103.
It is made of the materials described below so that it has compatibility with both. The charge injection prevention layer 103 mainly has a function of effectively preventing charge from being injected into the amorphous layer 104 from the support 101 side. The amorphous layer 104 has a function of generating photocarriers in the layer 104 upon irradiation with sensitive light and transporting the photocarriers in a predetermined direction. The auxiliary layer in the present invention is made of silicon atoms (Si).
The base material is nitrogen atom (N), halogen atom (X), and optionally hydrogen atom (H) as constituent atoms, and the content of nitrogen atom (N) is C _(N).
is less than 30 atomic% (hereinafter referred to as “a
−(SiaN ₁ −a)b(H,X) ₁ −b”. However, it is composed of 0.6<a, 0.8≦b). The auxiliary layer composed of a-(SiaN ₁ -a) b(H,X) ₁ -b can be formed by glow discharge method, sputtering method, ion implantation method, ion plating method, or electron beam method. etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. It is relatively easy to control the manufacturing conditions for manufacturing a photoconductive member having the above-mentioned photoconductive member. The glow discharge method or the sputtering method is preferably employed because of the advantages that nitrogen atoms and halogen atoms can be easily introduced into the auxiliary layer to be produced together with silicon atoms. Furthermore, in the present invention, the auxiliary layer may be formed by using both the glow discharge method and the sputtering method within the same apparatus system. To form the auxiliary layer by glow discharge method,
The raw material gas for forming a-(SiaN _{1 -a} ) b(H, a-(SiaN ₁ -a)b(H,X) _1-
It is sufficient to deposit b. In the present invention, a-(SiaN ₁ -a) b(H,X) ₁
As the raw material gas for forming -b, most gaseous substances containing at least one of Si, N, and X as a constituent atom or gasified substances that can be gasified can be used. When using a raw material gas containing Si as one of Si, N, and X, for example, one raw material gas containing Si, one containing N, and one containing X. Either a raw material gas containing Si atoms is mixed at a desired mixing ratio, or a raw material gas containing Si atoms and a raw material gas containing N and X atoms are mixed at a desired mixing ratio. They can be used by mixing in different ratios. Alternatively, a raw material gas containing Si and X as constituent atoms may be mixed with a raw material gas containing N as constituent atoms. In the present invention, preferred halogen atoms X are F, Cl, Br, and I, with F and Cl being particularly preferred. In the present invention, the auxiliary layer is composed of an amorphous material containing silicon atoms, nitrogen atoms, and halogen atoms, but as described above, the auxiliary layer may further contain hydrogen atoms. I can do it. The inclusion of hydrogen atoms in the auxiliary layer is advantageous in terms of production costs, since it is possible to share some of the raw material gas types when forming a continuous layer with the charge injection prevention layer and the amorphous layer. be. In the present invention, starting materials that can be used as raw material gases that are effectively used to form the auxiliary layer include those that are in a gaseous state at room temperature and normal pressure, or substances that can be easily gasified. . Examples of starting materials for forming such an auxiliary layer include nitrogen, nitrides, nitrogen compounds such as fluorinated nitrogen and azides, simple halogens, hydrogen halides,
Examples include interhalogen compounds, silicon halides, halogen-substituted silicon hydrides, and silicon hydrides. Specifically, nitrogen (N ₂ ), nitrogen compounds such as ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ),
Nitrogen trifluoride (F ₃ N), nitrogen tetrafluoride (F ₄ N ₂ ), hydrogen azide (HN ₃ ), ammonium azide (NH ₄ N ₃ )
etc., halogen gases include fluorine, chlorine, bromine, and iodine; hydrogen halides include FH, HI, HCl, and HBr; halogen compounds include BrF, ClF, ClF ₃ , ClF ₅ , BrF ₅ , _BrF3 ,
IF ₇ , IF ₅ , ICl, IBr, silicon halide
SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiCl ₃ Br, SiCl ₂ Br ₂ ,
SiClBr ₃ , SiCl ₃ I, SiBr ₄ , halogen-substituted silicon hydrides include SiH ₂ F ₂ , SiH ₂ Cl ₂ , SiHCl ₃ ,
SiH ₃ Cl, SiH ₃ Br, SiH ₂ Br ₂ , SiHBr ₃ , examples of silicon hydride include silanes such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc. I can do it. These starting materials for forming the auxiliary layer are used in such a way that the auxiliary layer to be formed contains silicon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms as necessary in a predetermined composition ratio. They are selected and used as desired during layer formation. For example, SiH ₄ or Si ₂ H ₆ can easily contain silicon atoms and hydrogen atoms and form an auxiliary layer with desired characteristics, and N ₂ or NH ₃ can contain nitrogen atoms. SiF ₄ , SiH ₂ F ₂ , SiHCl ₃ , SiCl ₄ as substances containing halogen atoms,
The auxiliary layer can be formed by introducing SiH ₂ Cl ₂ , SiH ₃ Cl, or the like in a gaseous state at a predetermined mixing ratio into the system for forming the auxiliary layer and causing glow discharge. Alternatively, _the auxiliary layer to be formed may contain He, _Ne , Ne, It is also possible to form an auxiliary layer by introducing it together with a rare gas such as Ar into an apparatus system for forming an intermediate layer to generate glow discharge. To form the auxiliary layer by the sputtering method, target a high-purity single crystal or polycrystalline Si wafer, a Si ₃ N ₄ wafer, or a wafer formed by mixing Si and Si ₃ N ₄ , These may be carried out by sputtering in various gas atmospheres containing halogen atoms and, if necessary, hydrogen atoms as constituent elements. For example, if a Si wafer is used as a target, the raw material gas for introducing N and The Si wafer may be sputtered by forming plasma. Alternatively, a gas atmosphere containing at least halogen atoms can be created by using Si and Si ₃ N ₄ as separate targets or by using a single target formed by mixing Si and Si ₃ N ₄ . This is done by sputtering inside. N and X,
If necessary, the starting material for forming the auxiliary layer shown in the glow discharge example described above can be used as a material gas for introducing H as an effective material also in the case of sputtering. In the present invention, so-called rare gases such as He, Ne,
Ar and the like can be cited as suitable examples. a-(SiaN ₁ -a) constituting the auxiliary layer of the present invention
The function of _b (H, Since the auxiliary layer is a material, its manufacturing conditions are strictly selected and carefully formed so that the desired properties are provided to the auxiliary layer. a- having characteristics suitable for the purpose of the present invention;
( _{SiaN 1} -a)b (H, That is, a-(SiaN ₁ -a)b on the surface of the support
When forming an auxiliary layer consisting of ( _H , , a-(SiaN ₁ −
The temperature of the support during layer formation is strictly controlled so that a) b(H,X) ₁ -b can be formed as desired. In order to effectively achieve the desired purpose of the present invention, the temperature of the support when forming the auxiliary layer is appropriately selected in the optimum range according to the method of forming the auxiliary layer. The formation is usually carried out at temperatures between 50 and 350°C, preferably between 100 and 250°C. To form the auxiliary layer, it is possible 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. Because it is relatively easy to finely control the composition ratio of atoms that make up each layer and control the layer thickness compared to other methods,
It is advantageous to employ the glow discharge method or the sputtering method, but when forming an auxiliary layer using these layer formation methods, the discharge power and gas pressure during layer formation, as well as the support temperature described above, must be adjusted. is created a-
(SiaN ₁ -a)b(H,X) ₁ -b can be mentioned as an important factor that influences the characteristics. The discharge power conditions for effectively producing a-( _{SiaN 1} -a)b(H, Usually 1 to 300W, preferably 2 to 100W. The gas pressure in the deposition chamber is usually 0.01 to 5 Torr, preferably 0.1 Torr when layer formation is performed using the glow discharge method.
When forming a layer by sputtering at a pressure of about 0.5 Torr, it is usually 1×10 ^-3 to 5×
10 ^-2 Torr, preferably about 8 x 10 ^-3 to 3 x 10 ^-2 Torr. The amounts of nitrogen atoms and halogen atoms contained in the auxiliary layer in the photoconductive member of the present invention are set so that the auxiliary layer can obtain the desired characteristics to achieve the object of the present invention, as well as the conditions for producing the auxiliary layer. This is an important factor for The amount C _(N) of nitrogen atoms contained in the auxiliary layer in the present invention is usually within the above-mentioned value range, but if expressed in atomic%, it is preferably 1×10 ^-3
It is desirable that ≦C _(N) <30, more preferably 1≦C _(N) <30, optimally 10≦C _(N) <30. Further, the amount of halogen atoms (X) is preferably 1 to 1.
It is desirable that the amount is 20 atomic %, optimally 2 to 15 atomic %, and if hydrogen atoms (H) are included, the amount is preferably 19 atomic % or less, optimally 13 atomic % or less. is desirable. When expressed as a and b in a-( _SiaN1 -a)b(H,X) ₁ -b, the value of a is preferably 0.6<a≦0.99999, more preferably 0.6 <a
≦0.99, optimally 0.6<a≦0.9, the value of b is
Preferably 0.8≦b≦0.99, more preferably 0.85≦b≦
A value of 0.98 is desirable. The numerical range of the layer thickness of the auxiliary layer in the present invention is appropriately determined as desired so as to effectively achieve the object of the present invention. In order to effectively achieve the purpose of the present invention, the thickness of the auxiliary layer is usually 30 Å to 2 μ, preferably 40 Å to 1.5 μ, and most preferably 50 Å to 1.5 μ. It is. The charge injection prevention layer constituting the photoconductive member of the present invention has a silicon atom (Si) as its base material, and preferably contains atoms belonging to Group 3 of the periodic table (Group atoms) and hydrogen atoms (H) or halogen atoms. (X) or both of these as constituent atoms (hereinafter referred to as "a-Si(V,H,X)"), the layer thickness t and the number of group atoms in the layer The content C _(V) is
It can be appropriately determined as desired so that the object of the present invention can be effectively achieved. The layer thickness t of the charge injection prevention layer in the present invention is preferably 0.3 to 5μ, more preferably 0.5 to 2μ.
It is desirable that the content of group atoms is
C _(V) is preferably 1×10 ² to 1×
¹⁰⁵ atomic ppm, more preferably 5× ¹⁰² to 1
It is desirable to set it to ×10 ⁵ atomic ppm. In order to obtain a synergistic effect between the charge injection prevention layer and the auxiliary layer, it is preferable that the thickness of each layer and the content of Group Group atoms of the periodic table or nitrogen atoms be within the above ranges. This is important in order for the auxiliary layer to exhibit sufficient adhesion and for the charge injection prevention layer to exhibit sufficient charge injection prevention properties. Generally, when the charge injection prevention layer is made thinner, it is preferable to increase the amount of Group Group atoms in the periodic table, and when it is made thicker, it is preferable to contain fewer atoms, but in the present invention, the adhesion with the auxiliary layer and the electrical properties After careful consideration, the content of nitrogen atoms in the auxiliary layer was
By setting the thickness of the charge injection prevention layer to less than 30 atomic% and within the above-mentioned range, not only can improved adhesion and charge injection prevention properties be achieved even more synergistically, but also the photoconductive member It has been found that many of the properties required for this can be fully satisfied. In the present invention, the atoms belonging to group of the periodic table contained in the charge injection prevention layer are P (phosphorus), As (arsenic), Sb (antimony), Bi
(bismuth), etc., and P and As are particularly preferably used. 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, with fluorine and chlorine being particularly preferred. It can be mentioned as such. Glow discharge method, sputtering method, ion implantation method, ion plating method, electron beam method, etc. are used to form the charge injection prevention layer composed of a-Si (V, H, X). Can be mentioned. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, amount of equipment capital investment, manufacturing scale, and desired characteristics of the photoconductive member to be manufactured. Along with silicon atoms, it is relatively easy to control the manufacturing conditions for manufacturing photoconductive members having group atoms,
The glow discharge method or the sputtering method is preferably employed because of the advantages that hydrogen atoms (H) and halogen atoms (X) can be easily introduced into the charge injection prevention layer to be prepared as needed. 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, in order to form a charge injection prevention layer composed of a-Si (V, H, The raw material gas for introducing group atoms that can supply group atoms together with the raw material gas, and the raw material gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary, are kept under reduced pressure inside. a-Si (V, H, ) may be formed. In addition, when forming by a sputtering method, for example, when sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce group atoms. The source gas for sputtering may be introduced into the deposition chamber for sputtering together with a gas for introducing hydrogen atoms (H) and/or halogen atoms (X) as necessary. In the present invention, starting materials serving as raw material gases used to form the charge injection prevention layer include:
The following can be listed as valid: First, silicon hydride (silanes) in a gaseous state or that can be gasified, such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , etc., is effective as a starting material that becomes the raw material gas for Si supply. It is cited as a material used in the production of silicon, especially in terms of ease of layer creation work and good Si supply efficiency.
Preferred examples include SiH ₄ and Si ₂ H ₆ . By using these starting materials, it is possible to introduce H as well as Si into the auxiliary layer formed by appropriately selecting the layer forming conditions. In addition to the above-mentioned silicon hydride, effective starting materials that serve as raw material gas for supplying Si include silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom, specifically, for example,
Silicon halides such as SiF ₄ , Si ₂ F ₆ , SiCl ₄ , and SiBr ₄ can be mentioned as preferred, and furthermore,
SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂ Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ ,
Halogen-substituted silicon hydrides such as SiHBr ₃ and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituent elements are also cited as starting materials for supplying Si for forming an effective charge injection prevention layer. I can do things. When using these silicon compounds containing halogen atoms (X), as mentioned above, it is possible to introduce X together with Si into the charge injection prevention layer formed by appropriately selecting the layer formation conditions. I can do it. The silicon halide compound containing a hydrogen atom in the above-mentioned starting material is a hydrogen atom ( Since H) is also introduced, it is used as a suitable starting material for introducing a halogen atom (X) in the present invention. In the present invention, effective starting materials that serve as raw material gas for introducing halogen atoms (X) used when forming the auxiliary layer include, in addition to those listed above,
For example, halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
Interhalogen compounds such as IF ₇ , ICl, IBr, HF, HCl,
Examples include hydrogen halides such as HBr and HI. In order to structurally introduce group atoms into the charge injection prevention layer, during layer formation, a starting material for introducing group atoms is placed in a gaseous state in a deposition chamber, and other materials are used to form the charge injection prevention layer. It may be introduced together with the starting material. Possible starting materials for the introduction of group atoms include materials that are gaseous at room temperature and pressure, or
It is desirable to use a material that can be easily gasified at least under layer-forming conditions. As a starting material for the introduction of such group atoms,
Specifically, for introducing phosphorus atoms, PH ₃ ,
Hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PCl ₃ ,
Examples include phosphorus halides such as PCl ₅ , PBr ₃ , PBr ₅ , and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ ,
AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF ₅ , SbCl ₃ ,
SbCl ₅ , BiH ₃ , BiCl ₃ , BiBr ₃ and the like can also be mentioned as effective starting materials for the introduction of group atoms. In the present invention, the group atoms contained in the charge injection prevention layer in order to provide charge injection prevention properties are arranged in a plane substantially parallel to the layer thickness direction of the charge injection prevention layer (toward the surface of the support). In parallel planes) and in the layer thickness direction, it is preferable that the distribution be substantially uniform. In addition, when forming a charge injection prevention layer by a sputtering method, for example, when sputtering a target made of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, , the raw material gas for introducing group atom into hydrogen atom (H) introduction or/
They may be introduced into a vacuum deposition chamber where sputtering is performed together with a raw material gas for introducing halogen atoms (X). In the present invention, the content of group atoms introduced into the charge injection prevention layer is determined by the gas flow rate of the starting material for introducing group atoms introduced into the deposition chamber, the gas flow rate ratio, the discharge power, and the support. It can be arbitrarily controlled by controlling body temperature, pressure inside the deposition chamber, etc. In the present invention, the diluent gas used when forming the charge injection prevention layer by the glow discharge method or sputtering method is a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. In the present invention, to form an amorphous layer composed of a-Si(H,X), for example, a glow discharge method,
This is accomplished by a vacuum deposition method that utilizes a discharge phenomenon, such as a sputtering method or an ion plating method. For example, by glow discharge method, a-Si
To form an amorphous layer composed of (H,X),
Basically, in addition to the raw material gas for supplying Si that can supply silicon atoms (Si), the raw material gas for introducing hydrogen atoms (H) and/or for introducing halogen atoms (X) is deposited in which the internal pressure can be reduced. A-Si is introduced into a chamber to generate a glow discharge in the deposition chamber, and a-Si
A layer consisting of (H,X) may be formed. or,
For example, when forming by sputtering method,
When sputtering a target composed of Si in an atmosphere of an inert gas such as Ar or He or a mixed gas based on these gases, it is necessary to introduce hydrogen atoms (H) and/or halogen atoms (X). The gas may be introduced into a deposition chamber for sputtering. In the present invention, as the halogen atom (X) contained in the amorphous layer if necessary, the same halogen atoms (X) as mentioned in the case of the charge injection prevention layer can be mentioned. In the present invention, the raw material gases for supplying Si used to form the amorphous layer include SiH ₄ , Si ₂ H ₆ , and
Gaseous or gasifiable silicon hydrides (silanes) such as Si ₃ H ₈ and Si ₄ H ₁₀ can be used effectively, especially because of the ease of handling in the layer creation process,
SiH ₄ and Si ₂ H ₆ are preferred from the viewpoint of good Si supply efficiency. In the present invention, many halogen compounds are effective as the raw material gas for introducing halogen atoms used when forming the amorphous layer, as in the case of the charge injection prevention layer, such as halogen gas,
Preferred examples include gaseous or gasifiable halogen compounds such as halides, interhalogen compounds, and halogen-substituted silane derivatives. Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and whose constituent elements are a silicon atom (Si) and a halogen atom (X), can also be mentioned as an effective compound in the present invention. In the present invention, the conductive properties of the amorphous layer can be controlled as desired by containing a substance that controls the conductive properties. Examples of such substances include so-called impurities in the semiconductor field, and in the present invention, a-Si (H,
P-type impurities that give P-type conductivity characteristics to There are In (indium), Tl (thallium), etc., and B,
It is Ga. In the present invention, the content of the substance that controls the conduction properties contained in the amorphous layer depends on the conduction properties required for the amorphous layer or other layers provided in direct contact with the amorphous layer. In terms of organic relationships, such as the characteristics of
It can be selected as appropriate. In the present invention, the content of the substance controlling conduction properties contained in the amorphous layer is usually 0.001 to 1000 atomic ppm, preferably 0.05 to 1000 atomic ppm.
500atomic ppm, optimally 0.1-200atomic ppm
It is desirable that this is the case. To structurally introduce substances that control conduction properties, such as group atoms, into an amorphous layer, the starting material for introducing group atoms is introduced in a gaseous state into a deposition chamber during layer formation. It may be introduced together with other starting materials for forming a crystalline layer. As a starting material for introducing such group atoms, it is desirable to employ a material that is gaseous at room temperature and pressure, or that can be easily gasified at least under layer-forming conditions. Specifically, starting materials for introducing such group group atoms include B 2 H 6 , B ₂ H ₆ ,
B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , B ₆ H ₁₄
and boron halides such as BF ₃ , BCl ₃ , BBr ₃ and the like. In addition, AlCl ₃ ,
GaCl ₃ , Ga(CH ₃ ) ₃ , InCl ₃ , TlCl ₃ and the like may also be mentioned. In the present invention, the amount of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the charge injection prevention layer and the amorphous layer of the photoconductive member to be formed, or the amount of hydrogen atoms (H) and halogen The sum of the amounts of atoms (X) (H+
X) is usually 1 to 40 atomic%, preferably 5
It is desirable that it be ~30 atomic%. In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) contained in the charge injection prevention layer or the amorphous layer, for example, the support temperature or/and the amount of hydrogen atoms (H) or halogen atoms can be controlled. The amount of the starting material used to contain the atoms (X) introduced into the deposition system, the discharge force, etc. may be controlled. In the present invention, a so-called rare gas, e.g.
Preferred examples include He, Ne, Ar, and the like. In the present invention, the thickness of the amorphous layer is determined appropriately depending on the characteristics required of the photoconductive member to be produced, but is usually 1 to 100 μm.
The thickness is preferably 1 to 80μ, most preferably 2 to 50μ. In the present invention, the support used may be either electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al,
Examples include metals such as Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof. As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side. For example, if it is glass, NiCr,
Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Conductivity can be imparted by providing a thin film made of Pd, In ₂ O ₃ , SnO 2 _, ITO (In ₂ O ₃ +SnO ₂ ), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al ,Ag,Pb,Zn,Ni,
A thin film of metal such as Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. is provided on the surface by vacuum evaporation, electron beam evaporation, sputtering, etc., or the surface is laminated with the metal, Conductivity is imparted to the surface. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined as desired. For example, the photoconductive member 100 in FIG. If it is used as a forming member, 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 determined appropriately so that a desired photoconductive member is formed, but if flexibility is required as a photoconductive member, the support can sufficiently function as a support. It is made as thin as possible within this range. However, in such cases, the thickness is usually 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. FIG. 2 shows the layer structure of another preferred embodiment of the photoconductive member of the present invention. The photoconductive member 200 shown in FIG. 2 differs from the photoconductive member 100 shown in FIG.
An upper auxiliary layer 204 is provided between the charge injection prevention layer 203 and the amorphous layer 205 exhibiting photoconductivity. That is, the photoconductive member 200 includes a support 201 and a lower auxiliary layer 2 laminated in this order on the support 201.
02, charge injection prevention layer 203, upper auxiliary layer 204
and an amorphous layer 205, the amorphous layer 205
has a free surface 206. Upper auxiliary layer 204
This strengthens the adhesion between the charge injection prevention layer 203 and the amorphous layer 205 and makes the electrical contact uniform at the contact interface between both layers. By providing the charge injection prevention layer 203, the layer quality of the charge injection prevention layer 203 is made strong. The lower auxiliary layer 202 and the upper auxiliary layer 204 constituting the photoconductive member 200 shown in FIG.
Auxiliary layer 1 constituting the photoconductive member 100 shown in the figure
Using the same amorphous material as in the case of 02, it is formed by the same layer forming procedure and conditions so as to provide similar properties. The charge injection prevention layer 203 and the amorphous layer 205 also have the same characteristics and functions as the charge injection prevention layer 103 and the amorphous layer 104 shown in FIG. 1, respectively. Formed by layer creation procedures and conditions. Next, an example of the method for manufacturing a photoconductive member of the present invention will be explained with reference to the drawings. FIG. 3 shows an example of a photoconductive member manufacturing apparatus. Gas cylinders 302 to 306 in the figure are sealed with gases used to form the respective layers of the present invention.
02 is SiH ₄ gas diluted with He (purity 99.999
%), hereinafter abbreviated as SiH ₄ /He. ) cylinder, 303 is
_PH3 gas diluted with He (purity 99.999% or less)
Abbreviated as B ₂ H ₆ /He. ) cylinder, 304 is NH ₃ gas (99.99% purity) cylinder, 305 is Ar gas cylinder,
306 is _SiF4 gas diluted with He (purity
99.999%, hereinafter abbreviated as SiF ₄ /He) cylinder. In order to flow these gases into the reaction chamber 301, valves 322 to 32 of gas cylinders 302 to 306 are used.
6. Confirm that the leak valve 335 is closed, and also confirm that the inflow valves 312 to 316, the outflow valves 317 to 321, and the auxiliary valve 332 are open, and first open the main valve 334 to react. The chamber 301 and the gas piping are evacuated. Next, when the reading on the vacuum gauge 336 reaches approximately 5×10 ^-6 torr, the auxiliary valve 332 and the inflow valve 31
2-316, close the outflow valves 317-321. Thereafter, a desired gas is introduced into the reaction chamber 301 by operating the valve of the gas pipe connected to the cylinder of the gas to be introduced into the reaction chamber 301 as prescribed. Next, an example of producing a photoconductive member having a structure similar to that shown in FIG. 1 will be outlined. To form an auxiliary layer on a predetermined support 337 by sputtering, the shutter 342 is first opened. All gas supply valves are once closed, and the reaction chamber 301 is evacuated by fully opening the main valve 334. A high purity silicon wafer 3 is placed on the electrode 341 to which high voltage power is applied.
42-1 and a high-purity Si ₃ N ₄ wafer 342-2 are placed as targets at a desired area ratio. Ar gas is introduced from the gas cylinder 305 and SiF ₄ /He gas is introduced from the gas cylinder 306 into the reaction chamber 301 by operating predetermined valves, and the main valve 334 is adjusted so that the internal pressure of the chamber is 0.05 to 1 torr.
Adjust. By turning on the high voltage power supply 340 and simultaneously sputtering the Si wafer 342-1 and the Si ₃ N ₄ wafer 342-2, an auxiliary layer made of an amorphous material made of silicon atoms and nitrogen atoms is formed on the support 337. can be formed on top.
During layer formation, the support 337 is heated by a heater 338.
is heated to the desired temperature. When forming the auxiliary layer by the glow discharge method, each valve is operated to discharge water from the cylinder 302.
SiH ₄ /He gas, NH ₃ gas from cylinder 304, and SiF ₄ /He gas from cylinder 306, respectively.
An auxiliary layer can be formed on the support by introducing it into the reaction chamber 301 at a desired flow rate and performing glow discharge for a desired time. Next, a charge injection prevention layer is formed on the auxiliary layer. 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 achieve the specified degree of vacuum. After that, the shutter 342 is closed, and SiH ₄ /He gas is supplied from the gas cylinder 302 to the gas cylinder 303.
PH ₃ /He gas from valves 322 and 32, respectively.
3 and set the pressure of the outlet pressure gauges 327 and 328 to 1.
Kg/cm ² , gradually open the inflow valves 312 and 313, and open the mass flow controllers 307 and 3.
08 respectively. Subsequently, the outflow valves 317 and 318 and the auxiliary valve 332 are gradually opened to allow the respective gases to flow into the reaction chamber 301. At this time, the outflow valve 31 is adjusted so that the ratio of SiH ₄ /He gas flow rate and PH ₃ /He gas flow rate becomes the desired value.
7 and 318, 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. Then, the temperature of the support body 337 is increased by the heating heater 33.
After confirming that the temperature is set in the range of 50 to 400° C. in step 8, the power source 340 is turned on and set to the desired power to generate glow discharge in the reaction chamber 301 and cause the temperature to rise above the support 337. A charge injection prevention layer is formed on the substrate. The amorphous layer exhibiting photoconductivity provided on the charge injection prevention layer is formed using, for example, SiH ₄ /He gas filled in the cylinder 302, in the same manner as in the case of the charge injection prevention layer described above. This can be done by following the steps below. In addition to SiH ₄ gas, Si ₂ H ₆ gas is particularly effective as the raw material gas used in forming the amorphous layer in order to improve the layer formation rate. Example 1 A layer was formed on an aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG. The electrophotographic image forming member thus obtained was placed in a copying machine, corona charged at 5 KV for 0.2 seconds, and a light image was irradiated. A tungsten lamp was used as the light source, and the light intensity was 1.0 lux·sec. The latent image is developed with a charged developer (containing toner and carrier), and the transferred image was checked for image defects (white spots on black backgrounds, etc.) transferred to ordinary paper, but there were no defects at all. The image quality was extremely good. Toner remaining on the image forming member without being transferred is cleaned by a rubber blade, and the toner is transferred to the next copying step. Even after repeating this process more than 100,000 times, image defects and
No layer peeling occurred at all.

[Table] Example 2 Si wafer as sputtering target
An electrophotographic image forming member was prepared in exactly the same manner as in Example 1 except that the content of nitrogen atoms in the auxiliary layer was changed by changing the area ratio of the Si ₃ N ₄ wafer. The results of evaluation in the same manner as above are shown below.

[Table] Example 3 An electrophotographic image forming member was prepared in the same manner as in Example 1 except for changing the thickness of the auxiliary layer, and the results of evaluation in the same manner as in Example 1 are as follows. show.

[Table] Example 4 An electrophotographic image forming member was produced in exactly the same manner as in Example 1, except that the layer thickness and boron content of the charge injection prevention layer were changed as follows. All results were good.

[Table] Example 5 A layer was formed on an aluminum substrate under the following conditions using the manufacturing apparatus shown in FIG. The thus obtained electrophotographic image forming member was evaluated in the same manner as in Example 1, and very good results were obtained.

[Table] Example 6 Using the manufacturing apparatus shown in FIG. 3, a layer was formed on a drum-shaped aluminum substrate in the same manner as in Example 1, except that the following conditions were used. The thus obtained electrophotographic image forming member was evaluated in the same manner as in Example 1, and very good results were obtained.

[Table] Example 7 In Example 1.5.6, the image forming member was formed according to the conditions and procedures in each example, except that the amorphous layer () was formed under the conditions shown in the table below. After creating and evaluating the same as in each example,
Good results were obtained.

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are schematic configuration diagrams showing the configuration of preferred embodiments of the photoconductive member of the present invention, respectively;
FIG. 3 is a schematic explanatory diagram showing an example of an apparatus for manufacturing the photoconductive member of the present invention. 100,200...Photoconductive member, 101,20
1...Support, 102,202,204...Auxiliary layer, 103,203...Charge injection prevention layer, 10
4,205...Amorphous layer, 105,206...Free surface.

Claims (1)

[Claims] 1. A support for a photoconductive member, a silicon atom as a matrix and a halogen atom as a constituent atom,
An auxiliary layer made of an amorphous material containing less than 30 atomic% of nitrogen atoms, and an amorphous material made of silicon atoms as a matrix and containing atoms belonging to group 3 of the periodic table as constituent atoms. Layer thickness 0.3~
A photoconductive member characterized by having a charge injection prevention layer of 5μ and an amorphous layer made of an amorphous material having silicon atoms as a matrix and exhibiting photoconductivity.