JPS6093447A - Photoconductive member - Google Patents

Abstract

PURPOSE:To provide a photoconductive member high in photoconductivity and SN ratio characteristics, and good in electric contact with a substrate by forming a photoconductive layer made of an amorphous material contg. Si and Ge and incorporating a substance for controlling conductive property and C element in said photoconductive layer. CONSTITUTION:The first photoconductive layer ( I ) 102 made of a-SiGe(H,X), and the second layer (II) 103 are formed on the substrate 101 for a photoconductive member. Since a layer region (PN) contg. a substance (C) for controlling conductive property, such as P type impurity giving P type conductivity or N type impurity giving N type conductivity, is formed on the side of the substrate 101, the conduction characteristics of this layer region can be optionally controlled as it is desired. C element is incorporated in the layer ( I ) 102 in order to enhance photosensitivity and dark resistance and improve adhesion between the substrate 101 and the layer ( I ).

Description

[Detailed description of the invention] The present invention is based on light (here, light in a broad sense, ultraviolet light).

The present invention relates to a photoconductive member that is sensitive to electromagnetic waves such as visible light, infrared light, X-rays, 7-rays, etc.

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 and has a high S/N ratio [photocurrent (■)/
It has a high dark current (Id), has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has a desired dark resistance value, and is harmless to the human body during use. Furthermore, solid-state imaging devices are required to have characteristics such as being able to easily process afterimages within a predetermined time. In the case of photographic imaging members, non-toxicity during use is an important consideration.

Based on these points, amorphous silicon (hereinafter referred to as a-Si) is a photoconductive material that has recently attracted attention.
No. 855,718 describes its application as an image forming member for electrophotography, and German Published Publication No. 2,933,411 describes its application to a photoelectric conversion/reading device.

However, a photoconductive member having a photoconductive layer composed of conventional a-8i has poor electrical, optical, and photoconductive properties such as dark resistance, photosensitivity, and photoresponsiveness, as well as moisture resistance, etc. The reality is that there is a need to improve overall characteristics in terms of usage environment characteristics and stability over time, and there are points that can be further improved.

For example, when applied to an electrophotographic image forming member, when trying to achieve high photosensitivity and high dark resistance at the same time, in the past, it has often been observed that residual potential remains during use, and this type of If a conductive member is used repeatedly for a long period of time, fatigue due to repeated use will accumulate, resulting in the so-called yeast phenomenon that causes an afterimage, or if used repeatedly at high speeds, the response will gradually decrease, etc. There were many cases where problems occurred @Furthermore, a-8
i has a relatively smaller absorption coefficient in the long wavelength region than in the long wavelength region compared to the short wavelength region in the visible light region, and is suitable for matching with semiconductor lasers currently in practical use and for normal use. When using a halogen lamp or a fluorescent pair as a light source, there is still room for improvement in that the light on the longer wavelength side cannot be used effectively.

Additionally, if the amount of light that reaches the support increases because the irradiated light is not absorbed sufficiently in the photoconductive layer, the support itself will reflect the light that has passed through the photoconductive layer. When the ratio is high, interference due to multiple reflections occurs within the photoconductive layer, which is one of the causes of "two spots" in the image.

This effect becomes more significant as the irradiation suit is made smaller in order to increase the resolution, and it becomes a major problem especially when a semiconductor laser is used as the light source.

Furthermore, when forming a photoconductive layer using an a-8t material, in order to improve its electrical and photoconductive properties, hydrogen atoms, fluorine atoms, chlorine atoms, and other hydrogen atoms, as well as electrically conductive Boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms 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 In some cases, problems may arise with the electrical or photoconductive properties of the formed layer.

That is, for example, the lifetime of photocarriers generated by light irradiation in the formed photoconductive layer may not be sufficient, or the injection of charges from the side of the support in a dark area may not be sufficiently prevented. This occurs in many cases.

Furthermore, if the layer thickness exceeds 10 microns or more, the layer may lift or peel off from the surface of the support, or the layer may peel off as the time elapses after it is left in the air after being removed from the vacuum deposition chamber for layer formation. We succeeded by causing phenomena 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, and there are points that need to be solved in terms of stability over time. .

Therefore, while efforts are being made to improve the properties of the a-8+ 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 focuses on the applicability and applicability of A-81 as a photoconductive member used in electrophotographic image forming members, solid-state imaging devices, reading devices, etc. As a result of comprehensive research and consideration from this perspective, we have discovered an amorphous material that has silicon atoms (St) and germanium atoms (Ge) as its base material and contains at least one of hydrogen atoms (6) or halogen atoms (a). , so-called hydrogenated amorphous silicon germanium, halogenated amorphous silicon germanium, or halogen-containing hydrogenated amorphous silicon germanium [hereinafter, these will be collectively referred to as r a -5iGe(H,X)J
A photoconductive member manufactured by specifying the structure of a photoconductive member having a first layer exhibiting photoconductivity consisting of [using] as explained hereinafter has extremely excellent properties in practical use. It is not a fool's errand; it is superior in all respects to conventional photoconductive materials, and it has particularly excellent properties as a photoconductive material for electrophotography, and on the long wavelength side. This is based on the discovery that it has excellent absorption spectrum characteristics.

The present invention has stable electrical, optical, and photoconductive properties at all times, and can be used in all environments with almost no restrictions on usage environments.In addition, it has excellent photosensitivity characteristics on the long wavelength side and is extremely resistant to light fatigue. The main object of the present invention is to provide a photoconductive member that is durable, does not cause deterioration even after repeated use, and has no or almost no residual potential observed.

Another object of the present invention is to provide a photoconductive member that has high photosensitivity in the entire visible light range, has excellent matching with semiconductor lasers in particular, and has fast photoresponse.

Another object of the present invention is to provide excellent adhesion between a layer designed 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 in structural arrangement, stable, sb, and has high layer quality.

Another object of the present invention is to maintain charge retention during charging processing for electrostatic image formation to such an extent that ordinary electrophotography can be applied very effectively when applied as an image forming member for electrophotography. It is an object of the present invention to provide a photoconductive member which has sufficient performance and excellent electrophotographic properties with almost no deterioration of the properties observed even in a humid atmosphere.

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

Yet another object of the present invention is high photosensitivity.

It is also an object to provide a photoconductive member having high signal-to-noise ratio characteristics and good electrical contact with the support.

The photoconductive member of the present invention includes a support for the photoconductive member, a photoconductive first layer made of an amorphous material containing silicon atoms and germanium atoms, and a photoconductive first layer made of an amorphous material containing silicon atoms and germanium atoms. a second layer made of an amorphous material containing a material, and a light-receiving layer made of a second layer made of an amorphous material, the second layer containing a substance controlling conductivity and unevenly distributed on the support side. It is characterized by having a layer region containing carbon atoms and containing carbon atoms.

The photoconductive member of the present invention designed to have the above-described layer structure can solve all of the problems described above, and has extremely excellent electrical, optical, and photoconductive properties. Indicates pressure resistance and usage environment characteristics.

In particular, when applied as an image forming member for electrophotography, there is no influence of residual potential on image formation, its electrical characteristics are stable, and it has high sensitivity and a high signal-to-noise ratio. Therefore, it has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear halftones, and high resolution.

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

Further, the photoconductive member of the present invention has high photosensitivity in the entire visible light range, is particularly excellent in matching with semiconductor lasers, and has fast photoresponse.

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

FIG. 1 is a schematic structural diagram schematically shown to explain the layer structure of a photoconductive member according to an embodiment of Ml of the present invention.

The photoconductive member 100 shown in FIG. 1 includes a support 101 for the photoconductive member, and a-5I
A first layer having photoconductivity consisting of Ge(I(,X)
1) 102 and a second layer (II) 103.

The germanium atoms contained in the first layer (1) 102 are continuously and uniformly distributed in the layer thickness direction of the first layer (1) 102 and in the in-plane direction parallel to the surface of the support 1010. It is contained in the first layer (1) 102 so that

In the photoconductive member of the present invention, in the first layer (1) containing germanium atoms, a layer region (PN) containing a substance (Q) that controls conduction properties is provided on the support side. Additionally, the conduction properties of the layer region (PN) can be controlled arbitrarily as desired.

Such substances (q) include so-called impurities in the semiconductor field, and in the present invention, a-8iGe (H,
), a p-type impurity that gives p-type conductivity characteristics and an n-type impurity that gives n-type conductivity characteristics can be mentioned.

Specifically, as the p-type impurity, atoms belonging to Group ■ of the periodic table (Group ■ atoms), such as B (boron), At
(aluminum), Ga (gallium).

In (indium) l Tt (thallium), etc.
Particularly preferably used are B and Ga.

Examples of n-type impurities include atoms belonging to group V of the periodic table (group V atoms), such as P (phosphorus), As (arsenic),
Examples include Sb (antimony) + 1st (bismuth), and particularly preferably used are P, As, and the like.

In the present invention, the content of the substance that controls the conduction properties contained in the layer region (PN) provided in the first layer (1) depends on the conduction properties required for the layer region (PN), Alternatively, the layer region (PN) can be appropriately selected depending on the organic relationship, such as the relationship with the characteristics at the contact interface with the support provided in direct contact with the layer region (PN).

Furthermore, the conduction characteristics are controlled by taking into consideration the characteristics of other layer regions provided in direct contact with the layer region (PN) and the relationship with the characteristics at the contact interface with the other layer regions. The content of the substance is selected appropriately.

In the present invention, the content of the substance controlling the conductive properties contained in the layer region (PN) is preferably 0.0
1 to 5 X 10' atomic ppm, preferably 0.5 to I X I O' atomic ppm
, most preferably 1 to 5×10' atomic ppm.

In the present invention, the content of the substance controlling the conduction properties in the layer region (PN) containing the substance.

Preferably 30 atomic ppm or more, more preferably 50 atomic ppm or more, optimally 1
For example, when the substance to be contained is the above-mentioned p-type impurity, when the free surface of the second layer (IQ is subjected to polar charging treatment, the second layer from the support side Injection of electrons into the layer (1) can be effectively prevented, and if the substance to be contained is the n-type impurity, the free surface of the second layer (II) can be effectively prevented. It can be shown that when subjected to charging treatment to the θ polarity, injection of holes from the support side into the first layer (1) is effectively prevented.

In the above case, the layer region C) excluding the layer region (PN) has a conduction polarity different from the polarity of the substance that governs the conduction characteristics contained in the layer region (PN). A substance that controls the characteristics may be contained, or a substance that controls the conduction characteristics of the same polarity may be contained in a much smaller amount than the actual amount contained in the layer region (PN). It is.

In such a case, the content of the substance controlling the conduction characteristics contained in the layer region ψ) is
) is determined as desired depending on the polarity and content of the substance contained in the substance, but preferably 0.0
01-1000 atomic ppm 1 more preferably 0.05-500 atomic ppm, optimally 0
．． It is desirable to set it as 1-200 atomic ppm.

In the present invention, when the layer region (PN) and the layer region (6) contain the same type of substance that controls conductivity, the content in the layer region (2) K is preferably 30%
It is desirable to set it to atomic ppm or less.

In addition to the above-mentioned cases, in the present invention, the first layer (1
) in which a layer region containing a substance controlling conductivity having one polarity and a layer region containing a substance controlling conductivity having the other polarity are arranged in such a way that they are in direct contact with each other. ,
It is also possible to provide a so-called depletion layer in the contact region. That is, for example, the layer region containing the p-type impurity and the layer region containing the n-type impurity are provided in the first layer (1) so as to be in direct contact with each other to form a so-called p-n junction. can be formed to provide a depletion layer.

In the present invention, the content of germanium atoms contained in the first layer (1) is determined as desired so as to effectively achieve the object of the present invention, but is preferably 1 to 9. .5 x 10' atomic 'ppm
, preferably 100 to 8.5
tomic ppm.

Optimally 500-7 X 10' atomic pp
It is preferable that it be m.

In the photoconductive member of the present invention, for the purpose of increasing photosensitivity and dark resistance, and further improving the adhesion between the support and the first layer (1), the first layer (1) is added. Carbon atoms are contained in the layer (1). The carbon atoms contained in the first layer (summer) may be evenly contained in the entire layer area of the first layer (1), or may be contained in a part of the first layer (1). It may be contained only in the layer region and unevenly distributed.

Further, the distribution state of carbon atoms may be such that the distribution concentration C (C) is uniform or non-uniform in the layer thickness direction of the first layer (1).

In the present invention, when the main purpose of the first layer (layer region C provided with carbon atoms) is to improve photosensitivity and dark resistance, the first layer (1 ), and the main purpose is to strengthen the adhesion between the support and the first layer (1),
It is provided so as to occupy the support side end layer region of the first layer (1).

In the former case, the content of carbon atoms contained in the layer region (C) is relatively low in order to maintain high photosensitivity, and in the latter case, to ensure enhanced adhesion with the support. It is desirable that the amount be relatively large in order to achieve this goal.

Also, for the purpose of achieving both the former and the latter at the same time,
The first layer (
1) at a relatively low concentration on the second layer (II) side, or the second layer (II) of the first layer (1).
It is sufficient to form a carbon atom distribution state in the layer region (Q) such that carbon atoms are not actively contained in the side surface layer region.

In the present invention, the layer region (
C) The content of carbon atoms in K is determined based on the characteristics required for the layer region (Q itself) or the layer region (when q is provided in direct contact with the support, the relationship between the layer region and the support). It can be selected as appropriate based on the organic relationship, such as the relationship with the properties at the contact interface.

In addition, in the case where another layer region is provided in direct contact with the layer region, the relationship with the characteristics of the other layer region and the characteristics at the contact interface with the other layer region. The carbon atom content is selected accordingly.

The amount of carbon atoms contained in the layer region (q is determined as desired depending on the properties required of the photoconductive member to be formed, but is preferably o, o o i ~ 50 at
omle%, preferably 0.002-40ato
m1c%s Optimal 0.003-30 atomi
It is desirable that it be set as e %.

In the present invention, even if the layer region n occupies the entire area of the 10th layer (1) or does not occupy the entire area of the 1st layer (1), When the proportion of the carbon atoms in the layer thickness T of the layer (1) is sufficiently large, it is desirable that the upper limit of the content of carbon atoms contained in the layer region (C) is sufficiently smaller than the above value.

In the case of the present invention, the layer thickness Tc of the layer region C) is the same as that of the first layer (
When the ratio of 1) to the layer thickness T is two-fifths or more, the upper limit of the amount of carbon atoms contained in the layer region 0 is preferably 30 atomic units or less, which is better. Preferably 20 atomic% or less, optimally 10 atomic%
It is desirable that the content be less than 1e% of atoms.

2 to 10 show typical examples of the distribution state of carbon atoms contained in the layer region (Q) of the photoconductive member of the present invention in the layer thickness direction.

In FIG. 2 to FIG. 1θ, the horizontal axis represents the carbon atom distribution concentration C (C), and the vertical axis represents the layer region (layer thickness of Q, tB
indicates the position of the end surface of the layer region (Q) on the support side, and tT indicates the position of the end surface of the layer region (C) on the opposite side to the support side. That is, the layer region containing carbon atoms (q indicates the position of the end surface of the layer region (C) on the side of tB) Layer formation is performed closer to the tT side.

FIG. 2 shows a first typical example of the distribution state of carbon atoms contained in the layer region (Q) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position tB where the surface where the layer region (C) containing carbon atoms is formed and the surface of the layer region (C) contact, the carbon atoms While the distribution concentration C (C) takes a constant value C1, it is contained in the layer region (C) where carbon atoms are formed, and gradually increases from the concentration C2 to the interface position tT at the position t. has been continuously decreased. At the interface position tT, the distribution concentration of carbon atoms C (Q is assumed to be C3).

In the example shown in FIG. 3, the distribution concentration C of the contained carbon atoms is C4 from position tB to position tTK.
The concentration decreases gradually and continuously from C5 to C5 at position t7.
The distribution state is formed as follows.

In the case of Fig. 4, the distribution concentration C (C) of carbon atoms is kept at a constant value c6 from position tB to multiple positions t2, and gradually and continuously decreases between position t2 and position tT. At the position tT, the distribution concentration C (C') is substantially zero (substantially zero here means that it is less than the detection limit amount).

In the case of FIG. 5, the distribution concentration C (C) of carbon atoms is gradually decreased from the concentration c8 from the position tB to the multi-position tT, and becomes substantially zero at the position tT. There is.

In the example shown in the M6 diagram, the distribution concentration C of carbon atoms is
Between position tB and position t3, the density is a constant value C2, and at position tT, the density is C1°. position t
3 and position tT, the distribution density c (C') is reduced in order of magnitude from position t3 to position tTK.

In the example shown in FIG. 7, a constant value of concentration c11 is taken at a position t4t from the distribution density cc) line position tB, a constant value of concentration c11 is taken from the position t4 to a position tTi, and a concentration C13 from 2 to 2.
It is assumed that the distribution state decreases in order of - order.

In the example shown in FIG. 8, from the position tB to the multi-position tT, the distribution concentration C (C) of carbon atoms decreases linearly from the concentration C44 to substantially zero.

In FIG. 9, the distribution concentration C (C) of carbon atoms decreases linearly from the concentration C45 to the concentration C46 until the position 1tBJ reaches the position t5.
An example is shown in which the density C16 is set to a constant value between .

In the example shown in FIG. 10, the distribution concentration C (C) of carbon atoms is C17 at position tB, and the concentration C17 is at position tB.
Until reaching 6, the concentration C47 is gradually decreased at first, and then rapidly decreased near the position t6, and becomes the concentration C18 at the position t6.

Between position t6 and position t7, the concentration is decreased rapidly at first, and then gradually decreased to C1 at position t7, and between position t7 and position t8, the concentration is extremely low. The concentration is gradually decreased and reaches the concentration C2o at position t8. Between position t8 and position t7,
[concentration C20] is decreased according to a curve shaped as shown in the figure so as to become substantially zero.

As described above with reference to FIGS. 2 to 10, some typical examples of the distribution state of carbon atoms contained in layer region 0 in the layer thickness direction, in the present invention, on the support side ,
It has a portion with a high distribution concentration C (C) of carbon atoms, and the interface t
On the T side, it is preferable that the distribution state of carbon atoms is provided in the layer region (0) in which the distribution concentration C is considerably lower than that on the support side.

In the present invention, the first layer (1) includes a layer region containing carbon atoms, and as described above, a localized region Φ containing carbon atoms at a relatively high concentration toward the support side. It is desirable that the sand be deposited as having the following properties, and in this case, the adhesion between the support and the first layer (1) can be further improved.

The localized region (B) is desirably provided within 5 μ of the interface position tB, if explained using the symbols shown in FIGS. 2 to 10.

In the present invention, the localized region (B) is located at the interface position t
It may be the entire layer region (LT) with a thickness of up to 5 μm across B, or it may be a part of the layer region (LT).

Whether the localized region (B) is a part or all of the layer region (LT) is determined as appropriate depending on the characteristics required of the first layer (1) to be formed.

The localized region (B) has a distribution state of carbon atoms contained therein in the layer thickness direction, and the maximum value Cmax of the distribution concentration C (C) of carbon atoms is preferably 500 atomlc p
pm or more, more preferably 800 atomlc ppm
As mentioned above, it is desirable that the layers be formed so that the distribution state is optimally 1000 atomic ppm or more.

That is, in the present invention, the layer region (C) containing carbon atoms has a layer thickness of within 5 μm from the support side (5 μm from tB).
It is desirable to form the layer so that the maximum value Cmax of the distribution concentration C) exists in the layer region) having a thickness of μ.

In the present invention, specific examples of the halogen atom (3) contained in the first layer (1) if necessary include fluorine, chlorine, bromine, and iodine, particularly heptafluorine, chlorine, etc. can be mentioned as suitable.

In the present invention, in order to form No. 10R (1) composed of a-81Ge(H, It is made by a vacuum deposition method.

For example, a-8IGe (II
,
(e) The raw material gas for supply and, if necessary, the raw material gas for introducing hydrogen atoms (σl) and/or the raw material gas for introducing halogen atoms (a) in a deposition chamber in which the internal pressure can be reduced to a desired gas pressure state. The a-SiGa(H, In addition, when forming by sputtering method, for example, Ar, He material active gas is used to form a target composed of St in an atmosphere of a mixed gas containing these gases as a base.
Alternatively, using two targets consisting of this target and Ge, or using a mixed target of SI and Ge, diluted with a diluent gas such as He or Ar as necessary. A raw material gas for supplying Ge, if necessary, a gas for introducing hydrogen atoms) and/or a gas for introducing halogen atoms (a) is introduced into the sputtering deposition chamber to form a plasma atmosphere of the desired gas. At the same time, the target may be sputtered while controlling the gas flow rate of the raw material gas for supplying Ge according to a desired rate of change curve.

In the case of the ion silating method, for example, polycrystalline silicon or recrystalline silicon and polycrystalline germanium or recrystalline germanium are respectively accommodated as evaporation sources, and the evaporation sources are heated using a resistance heating method, or Except for heating and evaporating by electron beam method (EB method) etc. and passing the flying evaporated material through the desired gas plasma atmosphere,
This can be done in the same manner as in the sputtering method.

Substances that can be combined with the raw material gas for 81 supply used in Mizumoto IN include Sil'14.5I2H6,51
3H8゜5i4H,. Silicon hydride (7 series) in a gaseous state or which can be gasified, such as , 5t2T (6 is preferred).

As a material that can be used as a raw material gas for supplying Ge, GeH
a + Gs 2H6, Ge 5Ha + Ge 4
H10, Go 5H12, Ge 6H+ 4゜Ge,
Germanium hydrides in a gaseous state or that can be gasified, such as Hlt, + GeaH4a, and GeqH2o, can be effectively used, especially in terms of ease of handling during layer creation work, good Ge supply efficiency, etc. , GeH4+
Preferable examples include Ge2H6 and Ge3HB.

Effective raw material gases for introducing halogen atoms (used in the present invention) include many compounds such as halogen gas, halogen compounds, interhalogen compounds, and silane derivatives substituted with halogen. Preferable examples include compounds in a gaseous state or which can be gasified.

Further, silicon hydride compounds containing nitrogen atoms, which are in a gaseous state or can be gasified and which have silicon atoms and nitrogen atoms as constituent elements, can also be mentioned as being ineffective in the present invention.

Specific examples of chlorine compounds that can be suitably used in the present invention include fluorine, chlorine, and bromine.

Halogen atom of iodine, BrF + CI-F + C
lF3. BrF5゜BrF IF, IF, IC
Examples include interhalogenated 3 I 3 7 compounds such as 4 and IBr.

A silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, is specifically, for example, 5kF4. Preferred examples include silicon halides such as Si2F6.5iC14,5IBr4.

When forming the characteristic photoconductive member of the present invention by a glow discharge method using a silicon compound containing such a nitrogen atom, a raw material gas that can supply Sl as well as a raw material gas for supplying Ge is used. a-8i containing 7.rogen atoms on the desired support without using hydrogen ion or silicon gas.
A first layer (1) of Ge can be formed.

According to the glow discharge method, the first layer containing halogen atoms (
When producing 1), basically, for example, silicon halide, which will be the raw material gas for s1 supply, germanium hydride, which will be the raw material gas for Ge supply, and gases such as H2, He, etc., are mixed in a predetermined manner. The first layer (
1) into a deposition chamber for forming the above gas, and by generating a glow discharge to form a plasma atmosphere of these gases, the 10th layer (1) can be formed on a desired support. However, in order to more easily control the introduction ratio of hydrogen atoms, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be further mixed with the gas in this tube to form a layer.

Moreover, each gas may be used not only as a substantially unique type, but also as a mixture of multiple types at a predetermined mixing ratio.

In order to introduce halogen atoms into the layer formed in both the S/E silating method and the ion silating method, a gas of the above-mentioned halogen compound or a silicon compound containing the above-mentioned halogen atoms is introduced into the deposition chamber. It is sufficient if a plasma atmosphere of the gas is formed by introducing the gas into the atmosphere.

In addition, when introducing hydrogen atoms, a raw material gas for hydrogen atom introduction, such as H2, or the above-mentioned silanes or/
Gases such as germanium hydride and the like may be introduced into the deposition chamber for snow e-tuttering to form a plasma atmosphere of the gases.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, but in addition, HF, HCl, HBr.

HI QIO hao ) I hydrogen chloride, 5IH2F2.5
iH212,5IH2C12゜5iHC13,SIH,
, Br2.5iHBr3, etc./'1lff Gen-substituted silicon hydride, and GeHF5 + Ge)12F2+ G
eH3F*GeHCl5'lGe12C421G
eHCl5 GeHI3. Hydrogenated germanium halide, such as GeH212, GeH, I, etc., with hydrogen atoms as one of the constituent elements.
GeF4. GeC4GeBr
GelGeF2. GaCl2. GeBr2. G
Gaseous or gasifiable substances such as germanium halides such as eI2 can also be mentioned as useful starting materials for forming the first layer (1).

Halides containing hydrogen atoms in these substances introduce halogen atoms into the layer at the same time as forming the first layer (I), and at the same time introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties. Therefore, in the present invention, it is used as a suitable raw material for introducing halogen.

To structurally introduce hydrogen atoms into the first layer (I),
In addition to the above, H2, or 5IH4, 5t2H6, St,
H6.

814H,. silicon hydride such as germanium or germanium compound for supplying Ge,
4, Ge2H6+ as sHe r Ge 4H1o
z Ge 5u, 2 + Ge 6H441Gs
7H1b r GeaHl B r Ge 9H20 etc. hydrogenated gel A/? This can also be achieved by causing discharge to occur by coexisting Ni and silicon or a silicon compound for supplying 81 in the deposition chamber.

In a preferred example of the present invention, the amount of hydrogen atoms (b), the amount of halogen atoms (a), or the amount of hydrogen atoms and halogen atoms contained in the first layer ω of the photoconductive member to be formed is The sum (H+X) is preferably 0.01 to 40 a
tomic%, preferably 0.05 to 3 g ato
mlc%, optimally 0.1-25 atomic%
It is desirable that this is done.

In order to control the amount of hydrogen atoms (b) and/or halogen atoms (a) contained in the first layer (1), for example, the support temperature or/and hydrogen atoms (000, or halogen atoms) can be controlled. The amount of the starting material used for inclusion into the deposition system, the discharge force, etc. may be controlled.

In order to structurally introduce a substance that controls conduction properties, for example, group Ⅰ atoms or group Ⅰ atoms into the layer region (PN) constituting the first layer (1), at the time of layer formation, The starting material for introducing group (I) atoms or 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 first layer (I). As a starting material for introducing such group m 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 such introduction of Group Ⅰ atoms include 1B2H6IB4H1o, B5H99B5,
Boron hydride such as H11°B6H1o, B6H12, B6H14, BF3°BCl2. Examples include boron halides such as BBrs +.

In addition, AtCl3. GaC45, Ga(CH3)3
．． InC1, TtCl.

etc. can also be mentioned.

In the present invention, the starting materials effectively used for the introduction of phosphorus atoms are PH3,
Hydrogen north neighbor such as P2H4, PH41, PF, PF5゜P
Cl3. PCl5. PBr, , PBr3. P
/S Cl generation ratio such as I, etc. In addition, A
sH2, AsF3. AsCA3゜AsBr, , A
sF5. SbH3,, SbF5, SbF5, 5
bC13,5bCt5°BiI3. BiCz, ,
BIBr3 and the like can also be mentioned as effective starting materials for group IV atoms.

In the present invention, in order to provide the layer region (C) containing carbon atoms in the first layer (1), a starting material for introducing carbon atoms is added during the formation of the first fi (1). It may be used together with the above-mentioned starting material for forming the first layer (I) and contained in the formed layer while controlling its amount. Layer area (
When a glow discharge method is used to form Q, a starting material for introducing carbon atoms is added to a material selected as desired from among the starting materials for forming the first layer (1) described above. As starting materials for such carbon atom introduction,
Most of the gaseous substances containing at least carbon atoms or the gasified substances that can be gasified can be used.

For example, a raw material gas containing silicon atoms (Si), a raw material gas containing carbon atoms (Q), and a raw material gas containing hydrogen atoms ◇υ or halogen atoms (a) as necessary. or a raw material gas containing silicon atoms (si) as constituent atoms and a raw material gas containing carbon atoms (C) and hydrogen atoms (6) in a desired mixing ratio. , this is also mixed at a desired mixing ratio, or a source gas containing silicon atoms (8k) and three constituent atoms: silicon atoms (Si), carbon atoms, and hydrogen atoms (b). It can be used by mixing with the raw material gas.

Alternatively, a raw material gas having carbon atoms (b) as its constituent atoms may be mixed with a raw material gas having silicon atoms (Si) and hydrogen atoms as constituent atoms.

Examples of those having C and II as constituent atoms include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, and the like.

Specifically, as a saturated hydrocarbon, methane (CH4)
+ ethane (C2H6), pu (ff/zon (C3HB)
+ ”-butane (n-c4■t+o) *Pentane (C5H12), as an ethylene hydrocarbon, ethylene (C2H4) *Zolopyrene CC3H6) r-butene-1 (C4■8) +butene-2 (C4H8) inbutylene (C4H6) + pentene (C5H4゜), as an acetylene hydrocarbon, acetylene (C2H2) +
Methyl acetylene (C3H4), butene (C4H6)
etc. can be mentioned.

In addition to these, alkyl silicides such as 5t(CH3)4.81(C2H5)4 can be cited as raw material gases containing 8% C and H as constituent atoms.

In the present invention, in order to further enhance the effect obtained with carbon atoms, the layer region (C) may contain oxygen atoms and/or nitrogen atoms in addition to carbon atoms. For example, oxygen (02), oxygen (0
3) +-nitrogen oxide (NO), nitrogen dioxide (NO2)
+-Nitrogen dioxide (N20) +Nitrogen sesquioxide (N203
), trinitrogen tetraoxide (N204), nitrogen pentoxide (N2O
5) rNitrogen trioxide (No, ), silicon atom (St
), an oxygen atom (0), and a hydrogen atom (6) as constituent atoms, for example, disiloxane (H3SiO8iH5),
) disiloxane (H,5iO8iH20SiH,)
and other lower siloxanes.

The starting materials that can be effectively used as the raw material gas for the atomic introduction of nitrogen used in forming the layer region (C) include those containing N as a constituent atom or containing N and H as constituent atoms. For example, nitrogen (N2), ammonia (Nf(3)
, hydrazine (H2NNH2), hydrogen azide (HN
3) Gaseous or gasifiable nitrogen such as ammonium azide (NH4N), nitrogen compounds such as nitrides and azides. In addition to this, in addition to introducing nitrogen atom toughness, nitrogen atoms (3) can also be introduced, so nitrogen trifluoride (Cv5N) + nitrogen tetrafluoride (F4
Examples include halogenated nitrogen compounds such as N2).

For sputtering, target a layer region containing carbon atoms (K forming 0 is an academic crystal or polycrystalline 81 wafer or C wafer -1 or a wafer containing a mixture of St and C, This can be done by sputtering in various gas atmospheres.

For example, if a Si wafer is used as a target, the raw material gas for introducing carbon atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluting gas as necessary and placed in a deposition chamber for sputtering. A gas plasma of these gases is formed to form the Si wafer.
The sputtering usage is good.

Alternatively, Sl and C may be used as separate targets, or a mixed target of Sl and C may be used in an atmosphere of diluted gas as a snogger gas or This is accomplished by snogging in a gas atmosphere containing at least hydrogen atoms (1) and/or halogen atoms (1) as constituent atoms. As the raw material gas for carbon atom introduction, the raw material gas for carbon atom introduction in the raw material gas shown in the glow discharge example mentioned above is used.
In the present invention for sputtering, when forming the first layer (summer), if a layer region (Q) containing carbon atoms is provided, the layer region (C
) to obtain a desired distribution state in the layer thickness direction (depth
To form a layer region (Q profile),
In the case of glow discharge, a gas as a starting material for introducing carbon atoms whose distribution concentration C (C) is to be changed is introduced into the deposition chamber while the gas flow rate is appropriately changed according to a desired rate of change curve. be done. For example, the opening of a predetermined needle valve provided in the middle of the gas flow path system may be gradually changed by any commonly used method such as manually or by using an externally driven motor. At this time, the rate of change in the flow rate does not need to be linear; for example, a microcomputer or the like can be used to control the flow rate according to a rate-of-change curve designed in advance to obtain a desired content rate curve. When the layer region (Q) is formed by the snogtuttering method, the distribution concentration C ((1'l) of carbon atoms in the layer thickness direction is changed to obtain the desired distribution state ( In order to form a depth profile, first, as in the case of the glow discharge method, the starting material for introducing carbon atoms is used in a gaseous state, and the gas flow rate when introducing the gas into the deposition chamber is adjusted. This can be done by changing the value as desired.

Secondly, the target for sputtering is made of, for example, Si.
If you use a mixed target of and C,
This is achieved by changing the mixing ratio of St and C in advance in the layer thickness direction of the target.

The layer thickness of the 10th layer (1) in the photoconductive member of the present invention is:
In order to efficiently transport the photocarriers generated in the first layer (1), the method is suitably adjusted as desired, preferably from 1 to 100μ, more preferably from 1 to 80μ, most preferably from 2μ.
It is desirable that the thickness be ~50μ.

In the photoconductive member 100 shown in FIG. 1, a second layer (II) 10 is formed on a first layer (1) 102.
3 has a free surface 104, which is provided mainly to achieve the objectives of the present invention in terms of moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

Furthermore, in the present invention, since each of the amorphous materials constituting the first layer Q) 102 and the second layer (n) 103 has a common constituent element of silicon atoms, The laminated interface is sufficiently acidified to ensure chemical stability.

The second layer ([[) in the present invention is silicon atoms (s
l), oxygen atom (0), and hydrogen atom (6) if necessary
or/and an amorphous material containing a halogen atom (hereinafter referred to as
It is written as ra-(5iXO1x)y(FI+X)1-yJ. However, o<x, y<1).

&-(5txol-x)y(it+x)1-3' The second layer ω) composed of This is done using the rating method, etc. These manufacturing methods are selected and adopted as appropriate depending on factors such as manufacturing conditions, degree 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 desired properties, and it is easy to introduce oxygen atoms and halogen atoms together with silicon atoms into the second layer 01) to be manufactured. The glow discharge method or the sputtering method is preferably employed because of the advantages such as ease of use.

Furthermore, in the present invention, the second layer 01) may be formed using a glow discharge method and a sputtering method in the same apparatus system.

To form the second layer by glow discharge method a.
-(513CO1-x)y(LX)1-y The raw material gas for formation is mixed with dilution gas at a predetermined mixing ratio as needed, and introduced into the vacuum deposition chamber where the support is installed. , the introduced gas is turned into gas plasma by causing a glow discharge, and milk-(SixOl-x)y(ILX)1 is applied onto the first layer (1) already formed on the support.
-7 should be deposited.

In the present invention, a −(si, o+−y) (H+X
) As the atomic gas for forming 1-y, silicon atoms (S
Most of the gaseous substances or gasified substances that have at least one of the following: l), oxygen atom (O), hydrogen atom (6), and halogen atom (a). may be used.

Separate, 0,11. When using a raw material gas having SI as a constituent atom as one of or/and a raw material gas containing X as constituent atoms at a desired mixing ratio, or a raw material gas containing Sl as constituent atoms and a raw material gas containing 0 and H as constituent atoms. or/and a raw material gas containing O and X as constituent atoms, also mixed at a desired mixing ratio, or a raw material gas containing Sl as constituent atoms,
A raw material gas containing Si, O, and H as constituent atoms or a raw material gas containing St, O, and X as constituent atoms can be used in combination.

Also, separately, raw material gas KO whose constituent atoms are Si and H
A mixture of raw material gases having constituent atoms KO may be used, or a mixture of raw material gases having raw material gas KO containing Sl and X as constituent atoms may be used.

In the present invention, F, Ct, Br, I are preferable as the nitrogen atoms contained in the second layer 0,
Particularly desirable are F and ct.

In the present invention, substances that can be formed into a raw material gas that can be effectively used to form the second layer (2) include substances that are in a gaseous state at room temperature and normal pressure, or substances that can be easily gasified. be able to.

Further, when forming the second layer (2) by a sputtering method, for example, the following procedure is performed.

Firstly, when sputtering a target made of St in an atmosphere of a mixed gas containing an inert gas such as Ar or He or a gas such as Ar, there is a method for introducing oxygen atoms (D). Hydrogen atoms are added to the raw material gas as needed.
It may be introduced into a vacuum deposition chamber in which sputtering is performed together with a raw material gas for introduction and/or for introduction of atoms (a).

Secondly, S t as a target for sputtering method.
A second i formed by using a target made of 02, or a target made of Si and a target made of S to2, or a target made of SI J 8102. Oxygen atoms (0) can be introduced into (11). At this time, if the above-mentioned raw material gas for introducing oxygen atoms (0) is also used, the amount of oxygen atoms (O) introduced into the second layer (II) can be arbitrarily controlled by controlling its flow rate. It is easy to do.

The content of oxygen atoms (0) introduced into the second layer [1] can be determined by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber, or by controlling the flow rate when the raw material gas for introducing oxygen atoms (0) is introduced into the deposition chamber. atomic ratio) The proportion of oxygen atoms (0) contained in the target for introduction,
By adjusting the source for creating the target, or by performing both, it is possible to arbitrarily control the target as desired.

The starting material used as the raw material gas for supplying St used in the present invention is 5in4. Sf 2116. S
+', H8°Si2 horse. Silicon hydride (silanes) in a gaseous state or which can be gasified are effectively used, such as SiH4,812H6, in particular, from the viewpoint of ease of handling in one-layer production work and good Si supply efficiency. are listed as preferred.

Using these starting materials, it is possible to introduce H as well as [Sl] into the second layer ω) formed by appropriately selecting the layer forming conditions.

Effective starting materials that serve as raw material gas for S1 supply include:
In addition to the above-mentioned silicon hydride, silicon compounds containing a halogen atom (a), so-called halogen atom-substituted silane derivatives, specifically, for example, 5IF4゜512F6.5ICA
4. '5IBr4 and other silicon halides are preferred.

Furthermore, SiH2F2.5iH2I2.81H2C12
, 5iHC45゜5IH2Br2.5I) Halogen-substituted silicon hydrides such as IBr3, and other gaseous or gasifiable halides containing hydrogen atoms as one of their constituents are also effective second layers (for the formation of sea cucumbers). can be cited as a starting material for supplying St.

When using these silicon compounds containing halogen atoms, as mentioned above, by appropriately selecting the layer forming conditions,
X can be introduced together with St into the second M (II) formed.

Among the above-mentioned starting materials, the silicon halide compound containing a hydrogen atom is used to control electrical or photoelectric properties at the same time as introducing halogen atoms (a) into the layer when forming the second layer Q[). Since a very effective hydrogen atom (6) is also introduced, it is used as a suitable starting material for introducing a halogen atom (a) in the present invention.

In addition to the above-mentioned materials, effective starting materials that serve as raw material gases for introducing halogen atoms (a) used in forming the second layer (It) in the present invention include, for example, fluorine, chloride, Bromine, iodine halogen gas, BrF,
C1F, C6F3, BrF5BrF3. IF
3. IF, .

Interhalogen compounds such as IC1, IBr, HF, H,
Hydrogen halides such as C6゜1 (Br, HI, etc.) can be mentioned.

The starting materials that can be effectively used to form the starting material gas 2 for oxygen atoms used in forming 20rr11ω) include O as a constituent atom or N and 0. For example, oxygen (02) is used as a constituent atom.

Ozone (05), -nitrogen oxide (NO), nitrogen dioxide (N
o□), -nitrogen dioxide (N20), nitrogen sesquioxide (N
203) is trinitrogen tetroxide (N204) lnitrogen pentaoxide (N205) + nitrogen trioxide (NOs) s The constituent atoms are scricon atom (st), oxygen atom (0), and hydrogen atom (6), for example , disiloxane (H3810Si
H,), )disiloxane Cl4381081H20
Examples include lower siloxanes such as S II3).

In the present invention, the diluent gas used when forming the second layer (n) by the glow discharge method is a so-called rare gas, such as He.

Preferable examples include N@, Ar, and the like.

The second layer ω) according to the invention is carefully formed so that its required properties are provided as desired.

That is, a substance whose constituent atoms are Si, O1, H or/and X as required, has a structure ranging from crystalline to amorphous depending on the conditions of its creation, and has an electrical property of:
In the present invention, u-( Ss
The preparation conditions are strictly selected as desired so that xOl z)y(H+X)1-y is formed. For example, to provide the second layer (It) with the main purpose of improving electrical withstand voltage, IL - (S1x (h - x) y ('L
X) 1-F is made as a lrf quality material with pronounced electrically insulating behavior in the service environment.

In addition, if a second layer ω) is provided with the main purpose of improving the characteristics of continuous repeated use and the characteristics of the usage environment, the above-mentioned degree of electrical insulation will be relaxed to a certain extent, and the sensitivity to the irradiated light will be increased to a certain degree. As an amorphous material with a −(
stxot x)y(H+X)1y is created.

a −(Stxol-x)y(
a- on the surface of the second layer (II) consisting of H+X)1-y
When forming the second layer 0) consisting of (" Therefore, in the present invention, a-(S
It is desirable that the temperature of the support during layer formation be tightly controlled so that izol-x)y(H2X)1-y can be formed as desired.

In the present invention, the formation of the second layer 01) is carried out by selecting an appropriate optimum range in accordance with the method of forming the second layer (II) in order to effectively achieve the desired purpose. but preferably 20 to 400°C, more preferably 50 to 350°C
The temperature is preferably 100 to 300°C. To form the second layer (II), glow discharge method or Adoption of sputtering method is advantageous, but these layer forming methods are
When forming layer (II>), discharge at the time of layer formation, a-(S
It is one of the important factors that influences the characteristics of 1Xol x)y()LX)1-y.

a having the characteristics for achieving the object of the present invention;
-(ss, olJy (LX)
W, preferably 5.0 to 200W.

The gas pressure in the deposition chamber is preferably 0.01 to 1 Torr.
.

More preferably, it is about 0.1 to 0.5 Torr.

In the present invention, the desirable numerical ranges of the support temperature and discharge power for creating the second layer (II) include the values in the above ranges, but these layer creation factors can be determined independently. Rather than being determined separately, the factors for creating each layer are determined based on their mutual organic relationship so that a second layer (n) consisting of a-(SIXOlx)y(LX)1y with desired characteristics is formed. It is desirable to be able to determine the optimal value.

The amount of oxygen atoms contained in the second layer (n) in the photoconductive part of the present invention is determined according to the desired characteristics to achieve the object of the present invention, as well as the production conditions of the second layer (It). is an important factor in the formation of the second layer (II) obtained.

No. 20 scrap Ql) K in the present invention: The amount of oxygen atoms contained is determined as desired depending on the type of amorphous material constituting the second layer (IQ) and its properties. It is something.

That is, the general formula a-(Six01-x)y(I(*
The amorphous material represented by X)1-y can be roughly divided into
It is written as "a -8taO+-aJ. However, 0(a(1)
, composed of silicon atoms, oxygen atoms, and hydrogen atoms
quality material (hereinafter r a -(SibOl-b)cH
Note that Q(b, c(1), an amorphous material composed of silicon atoms, oxygen atoms, halogen atoms, and optionally hydrogen atoms (hereinafter referred to as r a -(Si
It is written as dO+-a )e (H,'X)1-eJ. However, it is classified as 0 (d, e<1).

Mizumoto BJ] K ite, second layer (II) is a-8ia0
1-a, the amount of oxygen atoms contained in the second layer (II) is preferably 0.33 to 0.99999, expressed as a in a-8ilO1-@. More preferably it is 0.5 to 0.99, most preferably 0.6 to 0.9.

In IJ11, the second layer (n) is 8-(S 1
b01-b) c[If composed of 1-c, the second 1m
The amount of oxygen atoms contained in (II) is a −(Sl
bal-b) cHt-e, b is preferably 0.33 to 0.99999, more preferably 0.5 to 0.
,9, optimally between 0.6 and 0.9.5, preferably 0.6
It is desirable that it be ~0.99, more preferably 0.65-0.98, optimally 0.7-0.95.

The second layer (II) is a −(81dO+−a)e(I
LX) 1-6, the second layer (It)
The content of oxygen atoms contained in a-(Si
When expressed as d and e in aO+-a)e(H+X)+-8, d is preferably 0.33 to 0.99999, more preferably 0.5 to 0.99, optimally 06 ~0.9, e is preferably 0.8 to 0.99, more preferably 0.82 to
It is desirable that it be 0.99, most preferably 0.85 to 0.98.

The number range of the layer thickness of the second layer (It) in the present invention is one of the important factors for effectively achieving the object of the present invention.

In order to effectively achieve the object of the present invention, it can be determined as desired depending on the intended purpose.

The thickness of the second layer (n) also depends on the amount of oxygen atoms contained in the layer ([[) and the thickness of the first layer (1)]. It needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for the layer region.

In addition, it is desirable to take into consideration economic efficiency, which takes into account productivity and mass production.

The thickness of the second layer (II) in the present invention is preferably 0.003 to 30μ, more preferably 0.004 to 30μ.
It is desirable that the thickness be 20μ, most preferably 0.005 to 10μ.

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

Cr, MO, Au, Nb, Ta, V, Ti, Pt, P
Examples include metals such as d and alloys thereof.

As the electrically insulating support, polyester, polyether/, polycarbonate, cellulose acetate, Δ? Lysolobilene, polyvinyl chloride, No.? vinylidene chloride,
Polystyrene eyes? Films or sheets of synthetic resin such as Liamide, glass, ceramics, 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 side.

For example, if it is glass, the surface is coated with Cr and At.

Cr, MO% Au, Ir, Nb, TaXV,
Ti, Pt, Pd, In2O,,5n02,I
Conductivity can be imparted by providing a fly film made of TO (In203 +5n02), etc., or if it is a synthetic resin film such as polyester film, NlCr
, At, Ag, Pb, Znt NiXAu,
Cr, Mo, Ir.

A thin film of metal such as NbXTa, V, Tl, 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. 1 may be used as an electrophotographic image forming member. If used for continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is appropriately determined so as to form a photoconductive member of the desired thickness, but if flexibility is required as a photoconductive member, the thickness of the support may be determined to ensure that it can fully perform its function as a support. It is made as thin as possible within the range. However, in such a case, the thickness is preferably 10 μm or more in view of manufacturing and handling of the support, mechanical strength, etc.

Next, an outline of an example of the method for manufacturing a photoconductive member of the present invention will be explained.

Figure filN11 shows an example of a photoconductive member manufacturing apparatus.
The raw material gases 1102 to 1106 in the figure are sealed to form the photoconductive member of the present invention. .999%, below 81H4/
It is abbreviated as He. ) cylinder, 1103 is G diluted with He.
eH4 gas (purity 99.999%, hereinafter referred to as G@■ (4/H
Abbreviated as e. ) 2 mp, 1104 is B diluted with Ile.
21 (6 gas (purity 99.9.9%, hereinafter B2ll6/
It is abbreviated as He. ) ZEN (,1105 is C2 (4 gas (purity 99.999 inches) di/4.1106 is B271 gas (purity 99.999 inches) - npe.

How to make these gases flow into the reaction chamber 1101? Valves 1122 to 1126 of valves 1102 to 1106
, make sure that the leak valve 1135 is closed, and also check that the inlet valves 1112 to 1116 and the outlet valve 11 are closed.
After confirming that 17 to 1121 and auxiliary valves 1132 and 1133 are open, first open the main valve 1134 to exhaust the reaction chamber 1101 and each gas pipe. Next, the vacuum gauge 1136 reads approximately 5 X 10-'torr.
At this point, the auxiliary valves 1132 and 1133 and the outflow valves 1117 to 1121 are closed.

Next, as an example of forming the first layer (1) on the silicone/goo-like substrate 1137, the gas cylinder 1102
) SiH4/Be gas, gas cylinder 1103 J) Ge
H4/He gas, gas cylinder 1104 B2H6/H
e gas, gas yR pump 1105 p Open valves 1122 to 1125 for C2H4 gas and check outlet pressure gauge 1127
The pressure at ~1130 is adjusted to I Ky/cm2, and the inflow valves 1112-1115 are gradually opened to flow into the mass flow controllers 1107-1110, respectively. Subsequently, the outflow valves 1117 to 1120 and the auxiliary valve 1132
are gradually opened to allow each gas to flow into the reaction chamber 1101. At this time, 5iH4/He gas flow rate and GeI(4/
The outflow valve 1117 is adjusted so that the ratio of He gas flow rate, B2H6/He gas flow rate, and C24 gas flow rate becomes a desired value.
-1120, and also adjust the opening of the main valve 1134 while checking the reading on the vacuum gauge 1136 so that the pressure inside the reaction chamber 1101 reaches the desired value. and the base 11
The temperature of 37 is approximately 50-40℃ by heating heater 1138.
After confirming that the temperature is set within the range of 0°C, the power supply 1140 is set to the desired power and the reaction chamber 1101 is turned on.
A glow discharge is generated within the substrate 1137, and the glow discharge is maintained for a desired time to form a desired layer thickness K on the substrate 1137 containing boron atoms (B) and carbon atoms (C). Structured layer regions (B, C) are formed.

At the stage when the layer region (BIC) has been formed to the desired layer thickness, the same conditions are applied except for completely closing each of the outflow/6 lubes 1119 and 1120 and changing the discharge conditions as necessary. By maintaining glow discharge for a desired time according to the procedure, boron atoms (B
) and carbon atom (0), a -S I
The formation of the first layer (1) is completed by forming an upper layer region composed of Ge (HlX).

When forming the first layer (I), after starting the layer formation,
After the desired time has elapsed, B2H6/■ is added to the deposition chamber.
By stopping the flow of Ie gas or C2H4 gas, the thicknesses of the layer region (B) containing boron atoms and the layer region (C) containing carbon atoms can be arbitrarily controlled.

Also, C2 to the deposition chamber 1101 according to the desired rate of change curve.
By controlling the gas flow rate of H4 gas, the layer region (
The distribution of carbon atoms contained in C) can be formed as desired.

To form the second layer 01) on the first layer (1) formed to a predetermined thickness as described above, use the same valve operation as when forming the first layer (1). , for example, by diluting each of 5IH4 gas and NO with a diluent gas such as He as necessary to generate glow discharge according to desired conditions. In order to contain halogen atoms in the second layer (n), for example, add SiF4 gas and No gas, or 5IT (4 gas) to this and form the second layer (II) in the same manner as above. It is accomplished by

It goes without saying that all the outflow valves other than the gas outflow valves necessary for forming each layer should be closed, and when forming each layer, the gas used to form the previous layer is not allowed to flow into the reaction chamber. In order to avoid gas from remaining in the gas piping leading from the outflow ports 1117 to 1121 to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary knobs 1132 and 1133 are opened, and the main valve 11 is closed.
34 to fully open the system to temporarily evacuate the system to a high vacuum, if necessary.

The amount of oxygen atoms contained in the second layer (II) can be determined by, for example, changing the flow rate ratio of SIH4 gas and No gas introduced into the reaction chamber 1101 in the case of glow discharge as desired, or When forming a layer by IR or tarring, when forming the target, use silicon powder and 5
It can be controlled as desired by changing the surface area ratio of the 102 plate or by changing the mixing ratio of silicon powder and Si02 powder and molding the target. Halogen atoms (3) contained in the second layer ■)
The amount of raw material gas used in the raw materials, such as S
This is accomplished by adjusting the flow rate when the IFa gas is introduced into the reaction chamber 1101.

Further, during layer formation, it is desirable that the base 1137 be rotated at a constant speed by a motor 1139 in order to ensure uniform layer formation.

Examples will be described below.

Example 1 A cylindrical At
A layer was formed on the substrate outside the yarn shown in Table 1 to obtain an electrophotographic imaging member.

The image forming member obtained in this way is installed in a charging exposure experiment apparatus; 5. Corona charging was performed with OKV for 0.3 hours, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light intensity of 2 tux-sec was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the imaging member by cascading a θ-charged developer (including toner and carrier) over the surface of the imaging member. When the toner image on the image forming member was transferred onto a transfer paper by corona charging at 5.0 KV, a clear high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 2 In Example 1, B2H6 (S
Each electrophotographic image forming member was produced under the same conditions as in Example 1, except that the flow rate for iH4+GeH4) was changed as shown in Table 2.

Regarding the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in the table were obtained.

Example 3 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 3.

Using each of the image forming members thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 3 were obtained.

Example 4 A cylinder-shaped At
Layers were formed on the substrate under the conditions shown in Table 4 to obtain an electrophotographic image forming member.

The image forming member thus obtained was placed in a charging exposure experiment apparatus and the image forming member was set at θ5. Corona charging was performed for 0.3 hours using OKV, and a light image was immediately irradiated. A light image was generated using a tungsten lamp light source, and a light amount of 2 Lux-(8) was irradiated through a transmission type test chart.

Immediately thereafter, a good toner image was obtained on the surface of the image forming member by cascading a charged developer (including toner and carrier) over the surface of the image forming member. The toner image on the imaging member is set at θ5. When transferred onto transfer paper using OKV's corona charging, a clear, high-density image with excellent resolution and good gradation reproducibility was obtained.

Example 5 In Example 4, when creating the first layer, (S
Each electrophotographic image forming member was produced under the same conditions as in Example 4, except that the flow rate for iH4+GeH4) was changed as shown in Table 5.

Regarding the image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1.
The results shown in the table were obtained.

Example 6 Electrophotographic image forming members were prepared in the same manner as in Example 1 except that the thickness of the first layer was changed as shown in Table 6.

For each image forming member thus obtained, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and the results shown in Table 6 were obtained.

Example 7 Using the manufacturing apparatus shown in FIG. 11, layers were formed on a cylindrical M substrate under the conditions shown in Tables 7 and 8 to produce an electrophotographic image forming member (sample point 701. 702) was obtained.

For each of the image forming members obtained in this way, a toner image was obtained on a transfer paper using the same method and conditions as in Example 1, and the image was evaluated. A density image was obtained.

Example 8 Layer formation was carried out in the same manner as in Example 1 except that the manufacturing apparatus shown in FIG. Each (sample edition 801~
803) was obtained.

For each of the image forming parts thus obtained, Example 1
When an image was formed on transfer paper under the same conditions and procedures as described above, an extremely clear image quality was obtained.

Example 9 In Example 8, B2H6 (S
iH4+GeH4) in Tables 12 to 14.
Each electrophotographic image forming member was produced under the same conditions as in Example 8 except for the changes shown in the table.

For each of the image forming members thus obtained, Example 1
When an image was formed on transfer paper under the same conditions and procedures as above, the results shown in Tables 12 to 14 were obtained.

Example 10 In Example IK, the light source was replaced with a tungsten lamp.
An electrophotograph created under the same toner image forming conditions as in Example 1, except that an electrostatic image was formed using a 10 nm GaA + semiconductor laser (10 mW). When the image quality of the toner-transferred image of the image forming member was evaluated, a clear, high-quality image with excellent resolution and good gradation reproducibility was obtained.

Example 11 An electrophotographic image was produced according to the same conditions and procedures as in each example of Example 1.4.7.8, except that the conditions for forming the second layer (It) were as shown in Table 15. Each of the forming members (sample A 15-101 to 15-108.15-401 to 15
-408,..., 15-803-1 to 15-803
-8 samples) were created.

Each of the electrophotographic image forming members thus obtained was individually placed in a copying machine, corona charged at e15 KV for 0.2 scc, and an optical image was projected. A tungsten lamp was used as the light source, and the light intensity was set to 1 and OAux.

The latent image was developed with a charged developer (containing toner and carrier) and transferred to regular paper.

The transferred image was extremely good. Toner that was not transferred and remained on the electrophotographic imaging member was cleaned with a rubber blade.

Even after repeating this process more than 100,000 times, no image deterioration was observed in any case.

Table 15A shows the results of the overall image quality evaluation of the transferred images of each sample and the evaluation of durability through repeated and continuous use.

Example 12 During the formation of the second layer aI), the content of silicon atoms and oxygen atoms in the second layer (II) was changed by changing the target area ratio of the mixed gas of Ar and No, the silicon wafer, and 8102. Each of the imaging members was made in exactly the same manner as in Example 1, except that the ratios were varied. For each of the image forming members thus obtained, the steps of image formation, development, and cleaning as described in Example 1 were repeated approximately 50,000 times, and then image evaluation was performed, and the results shown in Table 16 were obtained. Obtained.

Example 13 When forming the second layer (II), SiH4 gas and NOO
Each of the image forming members was prepared in the same manner as in Example 1, except that the content ratio of silicon atoms and oxygen atoms in the second layer (II) was changed by changing the flow rate ratio. For each image forming member thus obtained, the process up to transfer was repeated approximately 50,000 times using the method described in Example 1, and then image evaluation was performed, and the results shown in Table 17 were obtained. .

Example 14 When forming the second layer (2), the flow rate ratios of 5IH4 dregs, 5SF4 dregs, and NOO20 were changed, and the content ratio of silicon atoms and oxygen atoms in the second layer (2) was changed. ,
Each of the image forming members was created in exactly the same manner as in Example 1. Each image forming member thus obtained was subjected to the image forming, developing and cleaning steps as described in Example 1 for approximately 5 minutes.
After repeating this process 10,000 times, image evaluation was performed and the results shown in Table 18 were obtained.

Example 15 Each of the imaging members was made in exactly the same manner as in Example 1, except that the layer thickness of the second 71 (10) was changed. The process was repeated to obtain the results shown in Table 19.

Common layer forming conditions in the examples of the present invention shown in Table 19 and above are shown below.

Base temperature: Rumanium atom (Ge) containing layer...approximately 2
00℃ germanium atom (Ge) non-containing layer...approx. 25
0℃ discharge frequency: 13.56 MHz Reaction chamber pressure during reaction: 0.3'l'orr

[Brief explanation of drawings]

FIG. 1 is a schematic layer structure diagram for explaining the layer structure of the photoconductive member of the present invention, and FIGS. 2 to 10 respectively show the no region (
FIG. 11 is an explanatory diagram for explaining the distribution state of carbon atoms in C). be. 100... Photo N4 electric member 101... Support body 102
...First layer (I) 103...Second layer (n) 1
04...Free surface -□-→-C (C) 1111→-C -11→-C Procedural amendment Showa [? Poetry date in November 2017 #, +1; Manabu Shiga, Director General of the Office of the Commissioner of Public Administration, JI ) (16g) Canon Co., Ltd. 4, 211 people fF Place East, 111-ku Marunouchi 2-chome I] 6#2
Shigesu Building 3308, hli inside No. Marunouchi.Amendment as shown in the attachment.The following matters have been amended in the original application specification. Note 1, page 50, line 3, [0.5 to 0.9J] is corrected to ``0.5 to 0.99J.

Claims (5)

[Claims] (1) A support for a photoconductive member, a first layer exhibiting photoconductivity made of an amorphous material containing silicon atoms and germanium atoms, and an amorphous material containing silicon atoms and oxygen atoms. a second layer made of a material, the first layer contains a substance that controls conductivity, has a layer region unevenly distributed on the support side, and contains carbon atoms. A photoconductive member characterized by: (2) The photoconductive member according to claim 1, wherein the first layer contains hydrogen atoms. (3) The photoconductive member according to claim 1 or 2, wherein the first layer contains halogen atoms. (4) The photoconductive member according to claim 1, wherein the substance that controls conductivity is an atom belonging to Group Ⅰ of the periodic table. (5) The photoconductive device according to claim 1, wherein the substance controlling conductivity is an atom belonging to Group V of the periodic table.