JPS58163954A - Photoconductive material - Google Patents

Abstract

PURPOSE:To obtain a photoreceptor superio in photosensitivity, durability, etc., by forming on a conductive substrate a photoconductive amorphous Si layer having a layer region contg. O and an element of group V of the periodic table in a specified distribution, and an amorphous layer contg. Si and C in due order. CONSTITUTION:A photoconductive amorphous layer 102 contg. Si as a main component is formed on a conductive substrate 101. The layer 102 has a layer region 104 contg. an element of group V of the periodic table, such as P, in a uniform distribution on the side of the substrate 101, and a layer region 103 contg. O in a distribution rich on the side of the substrate 101 and decreasing in the reverse side direction, the region 103 being included on the substrate side, and further, a layer region 105 formed on the region 104, contg. no element of group V and no oxygen. An amorphous layer contg. Si and C is formed on the layer 102, thus obtaining an electrophotographic receptor 100 superior in durability, photosensitivity, resolution, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to light (here, light in a broad sense, ultraviolet light, fiJ
This invention relates to a light guide "#L member that is sensitive to 1 magnetic waves such as visible light, infrared light, X-rays, gamma rays, etc."

(A photoconductive material that forms a photoconductive layer in a solid-state imaging device, an electrophotographic image forming member in the image forming field, or a document reading device has a high sensitivity, a high signal-to-noise ratio [photocurrent (Ip)
/ Has a high dark current (Φ), has absorption spectrum characteristics that match the spectrum characteristics of the irradiated electromagnetic waves, has fast photoresponsiveness, has a dark resistance value of 1, and is harmless to the human body during use. In solid-state imaging devices, rainbows require characteristics such as 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 important.

Based on these points, amorphous silicon (hereinafter abbreviated as a-8i) is a light guide-11 material that has recently attracted attention. As an image forming member for single-child photography, German Publication (2) Publication No. 4953411 discloses a light/ridge conversion reader/device.
The application of \ is described.

A photoconductor "1 member having a photoconductive layer composed of conventional A-81" has excellent electrical, optical, photoconductive properties such as dark resistance value, photosensitivity, and photoresponsivity, and use environment characteristics. Although individual improvements have been made in terms of stability, stability over time, and durability, there are still areas that need further improvement in order to improve overall properties. This is the reality.

For example, when applied to an electrophotographic image forming member, if an attempt is made to achieve high light sensitivity and high dark resistance at the same time, in the past, it has been difficult to achieve high light sensitivity and high dark resistance. - It is often observed that when this type of photoconductive member is used repeatedly for a long period of time, fatigue due to repeated use may accumulate, resulting in inconveniences such as the so-called ghost phenomenon that causes afterimages. There were many points.

When forming a photoconductive layer using a-8L material, in order to improve its electrical and photoconductive properties, halogen atoms such as hydrogen atoms, fluorine atoms, chlorine atoms, etc. In addition, boron atoms, phosphorus atoms, etc. are contained in the photoconductive layer as constituent atoms to control the electrical conduction type, or other atoms are included in order to improve other properties. Depending on the method used, problems may arise in the electrical or photoconductive properties or voltage resistance 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 support side may not be sufficiently prevented in the dark area. There were cases where this occurred.

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

The present invention has been made in view of the above points, and is applicable to an electrophotographic image forming member and a solid-state imaging device for the a-8i.
From the viewpoint of applicability and applicability as a photoconductive member used in reading devices, etc., as a result of intensive research and study, we found that silicon atoms are used as a matrix,
An amorphous material containing at least either a hydrogen atom (H) or a halogen atom (X), such as hydrogenated amorphous silicon, halogenated amorphous silicon, or halogen-containing hydrogenated amorphous silicon [hereinafter referred to as a generic term for these] As a notation (a-81(H,X)
A photoconductive member designed and produced with a photoconductive layer having a photoconductive layer composed of a photoconductive layer (using a photoconductive layer) as described below has extremely excellent properties in practical use. Based on the fact that it has been found that it not only exhibits excellent properties, but also surpasses conventional photoconductive members in all respects, and in particular has extremely superior properties as a photoconductive member for electrophotography. ing.

The electrical, optical, and photoconductive properties of the present invention are almost unaffected by the usage environment, are always stable, and are extremely resistant to light fatigue.
Excellent durability with no deterioration even after repeated use.
The main object is to provide a photoconductive member in which no or almost no residual potential is observed (5).

Another object of the present invention is that when applied as an image forming member for electrophotography, it has sufficient load retention capacity during imperial processing for image formation, and that ordinary electrophotographic methods cannot be used. The object of the present invention is to provide a photoconductive member having excellent electrophotographic properties that can be applied to extremely high-efficiency applications.

Still another object of the present invention is to provide an entire light guide material 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 to provide a photoconductive member having high S degree properties, high 8N ratio characteristics, and pressure resistance.

The photoconductive member of the present invention comprises a support for the photoconductive member, an amorphous layer of photoconductivity made of an amorphous material containing silicon atoms as a matrix, and silicon atoms and carbon. and an amorphous layer composed of an amorphous material containing atoms, the amorphous layer being continuous in the layer thickness direction and on the side of the support. A first layer region containing oxygen atoms as constituent atoms and a second layer region containing atoms belonging to Group O V of the periodic table (Group O V atoms) as constituent atoms in a distribution state in which a large number of atoms are distributed. The first layer region is characterized in that the first layer region is present on the support side of the amorphous layer of the O.

The photoconductive member of the present invention designed to have the above-mentioned layer structure can solve all of the above-mentioned problems, and has extremely excellent electrical, optical, photoconductive properties, and 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, and its electrical characteristics are stable, high sensitivity, and has a high tones ratio. It has excellent light fatigue resistance and repeated use characteristics, and can stably and repeatedly produce high-quality images with high density, clear crosstones, and high resolution. .

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

(7) FIG. 1 is a schematic configuration diagram schematically shown to explain the layer configuration of the light guide member of the present invention.

The photoconductive member 100 shown in FIG. 1 is a photoconductive amorphous material consisting of a-8l (H, 102, and an amorphous layer (n) 105 made of an amorphous material containing silicon atoms and carbon atoms.

The amorphous layer (I) 102 is continuous in the layer thickness direction and is distributed more toward the support 101,
First layer region (0) containing oxygen atoms as constituent atoms
103 and a second layer region (V) 104 containing O-V group atoms as constituent atoms. In the example shown in FIG. 1, the first layer region (0
) 1o5 has a layer structure in which a portion of the second layer region (V) 104 is occupied, and the first layer region (0) 10! 1 and the second layer region (V) 104 is an amorphous layer (1) of O.
02 is unevenly distributed on the support body 101 side. Oxygen atoms and O group V atoms are not substantially included in the first layer region 105 on the amorphous layer (I) 102, and oxygen atoms are present in the first layer (8) region (0 ) Group O atoms in 103 are in the second layer region (V)
It is contained in 104. Of course, the first layer region (0) 1
03 also contains an O-group atom.

In the present invention, the above-mentioned layer structure is adopted because the first layer region (0) 105 has high dark resistance due to the inclusion of oxygen atoms, and the support 101 and the amorphous I@( I) 1
02, and the upper layer region 105 does not contain oxygen atoms to increase sensitivity. First layer area (0) 10! The oxygen atoms contained in the amorphous layer (I) 10 are continuously and non-uniformly distributed in the layer thickness direction, and the oxygen atoms contained in the support 101 and the amorphous layer (I) 10
In the present invention, the amorphous layer (I) 102 is contained in the first layer region (0) 105 in a substantially uniform distribution state in a plane parallel to the interface with the first layer (I) 102. A second layer region (V) 104 comprising gold and containing O-group atoms gold
The O-V group atoms contained in P (phosphorus), As (
arsenic), Sb (antimony), fli (bismuth)
etc., and particularly preferably used is ilt ” + A
It is a.

(9) In the present invention, the distribution state of the O-group atoms contained in the second layer region (V) 104 is substantially the same in the thickness direction and in a plane parallel to the surface of the support 1010. It is assumed that the distribution is uniform.

The layer thickness of the first layer region (0) 105 and the first layer region 105 is one of the important factors for effectively achieving the object of the present invention. There are a number of factors that require careful consideration in the design of the photoconductive member so that the desired properties are imparted to the photoconductor.

In the present invention, the upper limit of the layer thickness TB of the second layer region (V) 104 is usually 50μ or less, preferably 60μ or less, and the maximum dK is 10μ or less. That's the 4th thing. Moreover, the layer thickness T of the upper) region 105 is
The F limit is usually 0.5μ or more, preferably 1μ or more, and optimally 3μ or more.

The lower limit of the layer thickness TB of the second layer region (7) 104 and the upper limit of the layer thickness T of the upper layer region 105 are the characteristics required for both layer regions and the requirements for the entire amorphous (■) 102. Characteristics (10) and (10) are appropriately determined as desired when designing the light guide I4c member.

In the present invention, it is preferable that appropriate values are selected for the layer thickness TB and layer thickness T so as to satisfy the relationship TB/T≦1. In selecting the numerical values of layer thickness TB and layer thickness T, more preferably TB/
It is preferable that the values of layer thickness TB and layer thickness T be determined so that the relationship T≦0.9, optimally TB/T≦0.8, is satisfied.

In the photoconductive member of the present invention shown in FIG.
Although a layer region (0) 103 is formed, the first layer region (0) and the second layer region (cape) may be the same layer region.

Furthermore, a case where the second layer region (compartment) is formed within the first layer region (0) can also be cited as one of the preferred embodiments.

(11) of the oxygen atoms contained in the first 1-region (0)
) f is determined as desired depending on the characteristics required of the photoconductive member to be formed, but is usually 0.00.
1-50 atofnic%, preferably 0.002
~40 atomic %, optimally 0.006-30
It is preferable to set it to atomic%.

If the layer thickness TO of the first 1-region (0) is sufficiently thick or the ratio of the amorphous layer (I) to the total layer thickness exceeds two-fifths or more, the first The upper limit of the pupil of oxygen atoms contained in the layer region (0 nm is usually 30 at
omic Q% or less, preferably 20 atomlc% or less, optimally 10 atomiQ% or less
It's a beautiful thing.

In the present invention, the thickness of the amorphous JIL layer is usually 1 to 100 μm, preferably 1 μm, from the viewpoint of obtaining desired photographic properties and economical efficiency. ~80μ,
The optimum thickness is preferably 2 to 50μ.

2 to 10 show light 1 in the present invention.
1 A typical example of the distribution state of oxygen atoms in the layer thickness direction (1 direction) contained in the first layer region (0) constituting the amorphous layer (I) of the conductive member is shown. .

In the examples shown in FIGS. 2 to 10, even if the layer region (v) containing group O atoms is the same layer region as the 1- region (0), the layer region (0) 't - Even if it includes, or 1
- Since a part of the layer region of region (0) may be shared, in the following explanation, the layer region (V) containing O-V group atoms will not be particularly explained. Don't mention it unless necessary.

In FIGS. 2 to 10, the horizontal axis represents the distribution concentration C of oxygen atoms, and the vertical axis represents the layer region (0) that constitutes the amorphous layer exhibiting photoconductivity and contains oxygen atoms. Indicates the thickness TB, t
B indicates the position of the interface on the support side, and tT indicates the position of the interface on the opposite side to the support side. That is, in the layer region (0) containing oxygen atoms, the layer is formed from the tB side toward the tT side.

In the present invention, the layer region (o) containing oxygen atoms
C. It consists of a-81 (Hlx) that constitutes the light guide 11ts material, and occupies a part of the amorphous layer (I) of O that exhibits photoconductivity.

In the present invention, the layer region (0) includes the surface of the amorphous layer (I) on the support 101 side, as shown in the example of FIG. 1 (15). I) It is preferable to provide it in the lower layer region of 102.

FIG. 2 shows a first typical example of the distribution state of oxygen atoms contained in the layer region (0) in the layer thickness direction.

In the example shown in FIG. 2, from the interface position tB where the surface where the layer region (0) containing oxygen atoms is formed and the surface of the layer region (0) contact, the oxygen atoms are While the distributed concentration C takes a constant value of C4, it is contained in the layer region where oxygen atoms are formed, and from the position flt+, the distributed concentration C gradually decreases continuously from 02 until it reaches the interface position 1ttT. At the interface position ttT, the distribution concentration C of oxygen atoms is 05.

In the example shown in FIG. 3, the distribution concentration C of the contained oxygen atoms is C4 from position tB to position fttT.
A distribution state is formed in which the value gradually and continuously decreases to 05 at 1ttT.

In the case of Figure 4, from position 11tB to position t2 is (1
4) The distribution concentration of oxygen atoms is kept at a constant value O&''iC6, gradually and continuously decreases between the position t2 and the position 1ftT, and becomes substantially zero at the position dtT.

In the case of FIG. 5, the distribution concentration C of oxygen atoms is gradually decreased continuously from 08 from position tB to mtT, and becomes substantially zero at position tT.

In the example shown in Figure 6, the distribution of oxygen atoms once C is
Between position fitB and position tiLts, C? is a constant value, and is set as C1o in the place 1fitT.

Between the ai layer upper level 5 and the level 1ttT, the distribution C is linearly reduced from the level tts to the level ttT.

In the example shown in the off-diagram, the distribution concentration 9 is at 1lt
Ranked better than tB! Take a constant value t- of 011 up to 1t4, place 1
From tt4 to 1ttT, the distribution state decreases linearly from CI2 to 015.

In the example shown in FIG. 8, from position 1 ftB to position tT, the distribution concentration 0 of oxygen atoms decreases linearly from 014 to (15) zero.

In FIG. 9, from position 1 tB to position t5, the distribution concentration C of oxygen atoms decreases linearly from C15 to CI6, and between position If ts and position ttr, the distribution concentration C of oxygen atoms decreases in a linear manner from position tB to position t5. An example in which the value is set to a constant value is shown.

In the example shown in FIG. 10, the distribution concentration C of oxygen atoms is 017 at position tB, and decreases slowly from 017 until reaching position t6, and then decreases slowly at I6.
In the vicinity of the position t6, the value is rapidly decreased to 018 at the position t6.

Between position t6 and position t7, the distribution concentration C is initially rapidly decreased, and then gradually decreased to O+t at position t7, and between position t7 and position t8, It is gradually reduced very slowly until it reaches C2o at position t8. Between position t8 and position tT, the distribution density C is reduced from 02G to substantially 01fC according to a curved line as shown in the figure.

As described above, according to FIGS. 2 to 10, layer regions (0) (16
) As described in some of the typical examples of the distribution state of oxygen atoms contained in the 1-thickness direction, in the present invention, the support side has a portion with a high distribution concentration C of oxygen atoms,
On the interface I7 side, a layer region (Q) containing oxygen atoms in a distributed state having a portion where the distribution concentration C is relatively lower than that on the support side is provided in the amorphous layer (I). It is being

In the present invention, the layer region (0) containing oxygen atoms constituting the amorphous layer (I) contains oxygen atoms at a relatively high concentration toward the support side, as described above. It is preferable that the support be provided as having localized regions, and in this case, the adhesion between the support and the amorphous layer (I) can be further improved.

If the localized region (A) is explained using the symbols shown in FIGS. 2 to 10, it is desirable that the localized region (A) be provided within 5 μm from the interface position tB.

In the present invention, the localized region (A) is located at the interface position t
(17) Whether the localized region (A) is a part or all of the layer region LT depends on the formed amorphous layer (I). ) shall be regulated as appropriate according to the characteristics required.

The localized region (A) has the maximum distribution concentration of oxygen atoms Oma as the distribution state of the oxygen atoms contained therein in the layer thickness direction.
X is usually more than so atomic ppm,
It is desirable that the layer be formed so as to achieve a distribution state of preferably 800 atomic ppm or more, most preferably 1000 atomic ppm or more.

That is, in the present invention, the layer region (0) containing oxygen atoms is such that the maximum value 01naX of the distribution concentration C exists within 5 μm (layer region with a thickness of 5 μm from tB) in the layer 11 from the support side. It is desirable that it be formed as follows.

ff) In the present invention, the KMk of group O V atoms contained in the -'Im'tA region is determined as appropriate in accordance with the requirements so that the purpose of the present invention can be effectively achieved. Usually 30~5X10'atomiQ ppfn
, preferably 50 to I x 10' atoms (1
8) 1) pm % maximum 100~5 × 1
05 atomtc ppm is preferable.

In the light 4'#4 member of the present invention, when the photoconductive member is subjected to charging treatment, the second layer region (V) constituting a part of the amorphous layer (I) is , the layer area on the support side 2 (V
), and the thickness and characteristics of the Icd region provided directly on the second layer region (V). It is desirable that the layer thickness of V) is appropriately determined in accordance with Pfr 4 so that the above function is sufficiently achieved.

In the present invention, if the above points are mainly considered, the second
It is desirable that the layer thickness of the l-region (V) is normally 50A to 5μ, preferably 408 to 4μ, and optimally 508 to 6μ.

In the present invention, the amorphous layer (1) composed of a-81 (H, RI) is formed by a discharge method such as a glow radiation method, a sputtering method, or an ion blurring method. For example, by a glow discharge method, a-El
In order to form the O amorphous layer (1) composed of i(H,X), hydrogen atoms (H ) A raw material gas for introduction and/or for introduction of halogen atoms (X) is introduced into a deposition chamber whose interior can be reduced in pressure, and a glow discharge is generated in the deposition chamber. A layer consisting of a-8L(H,X) may be formed on the surface of the support. In addition, when forming by a sputtering method, for example, when sputtering a target composed of 81 in an atmosphere of an inert gas such as Ar, f(θ, etc.) or a mixed gas based on these gases, hydrogen atoms A gas for introducing (H) and/or halogen atoms (X) may be introduced into the deposition chamber of the sputtering method.

In the present invention, if necessary, the amorphous
The halogen atoms (X) contained in the layer (1) are as follows:
Specifically, fluorine, chlorine, bromine, and iodine can be removed (20), and fluorine and chlorine can be used as suitable materials to speed up the process.

The raw material gas for S1 supply used in the present invention includes 5 inches (4, Si2H6, Si, H8, 5i4H,
Silicon hydride in a gaseous state or which can be gasified (7-ranium) such as Si
Preferred examples include H4 and Si□H6.

Effective raw material gases for introducing halogen atoms used in the present invention include many halogenated gases, such as halogen gases, interhalogen compounds, and halogen-substituted silane derivatives. Or a halogen compound that can be gasified is preferably mentioned.

Further, a silicon compound containing a halogen atom, which is in a gaseous state or can be gasified and has a 7-licon atom and a halogen atom as its constituent elements, can also be mentioned as effective in the present invention.

Specifically, the halogenated (21) compounds that can be suitably used in the present invention include halogen gases of fluorine, chlorine, bromine, and iodine, BrF, OJF, OJF3°BrF
5. BrF, , Eng y2. Engineering 11P7 * I OJ
, IBr, and other interhalogen compounds.

Specifically, as a silicon compound containing a halogen atom, so-called a silane derivative substituted with a halogen atom, for example, 8
Preferred silicon halides include 1F4, 812F6, 5iOj4, 81f3r4@.

When employing such a silicon compound containing a halogen atom and forming the characteristic photoconductive member of the present invention by the C glow discharge method, silicon hydride gas is not used as a raw material gas capable of supplying Si. In either case, an amorphous layer (I) of a-8i containing halogen atoms can be formed on a predetermined support.

When forming an amorphous layer (I) of O containing halogen atoms according to the glow emission method, basically silicon halide gas, which is a raw material gas for supplying 81, and Lr r H2
A gas such as + Hθ is introduced into the deposition chamber in which an amorphous layer (I) of O is formed at a predetermined mixing ratio and in a gas flow pattern, and a glow is emitted to generate Vt gold. By forming a plasma atmosphere of such gases, it is possible to form O amorphous * Itlj (I) on a predetermined support, but in order to introduce hydrogen atoms, these gases may be further A layer may also be formed by mixing a predetermined amount of a silicon compound gas containing hydrogen atoms.

Father, each gas can be used not only individually but also in a mixture of multiple units at a predetermined mixing ratio.

An amorphous layer of a-sl (a, x) (I
) lf: To form, for example, in the case of a sputtering method, a target made of Sl is used, and this is sputtered in a predetermined gas plasma atmosphere. Single-crystal 7-licon is housed in a deposition boat as an evaporation source, and this silicon evaporation source is heated using a resistance heating method or an electron beam (
25) This can be carried out by heating and evaporating the flying evaporated material using the FB method or the like and passing it through a predetermined gas plasma atmosphere.

At this time, in order to introduce halogen atoms into the layer formed by either the sputtering method or the ion grating method, the above-mentioned halogen compound or the above-mentioned halogen gas containing the 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 introducing water atoms, such as H2 or the above-mentioned silica gas, is introduced into the deposition chamber for sputtering to create a plasma atmosphere of the gas. Just form it and sell it.

In the present invention, the above-mentioned halides or halogen-containing silicon compounds are effectively used as raw material gases for introducing halogen atoms, and in addition, HF, HO7j.

Hydrogen halides such as HBr, II, etc., 5in2F2.
5in (2r2゜5iH2C12,5IHOJ3.5i
Halogenated hydrogen atoms (24) such as H2Br2.131HBr, etc., which are in a gaseous state or can be gasified, and which have a hydrogen atom as one of their constituents are also effective as amorphous layers. (1) Can be mentioned as a starting material for formation.

Halides containing this many hydrogen atoms introduce hydrogen atoms, which are extremely effective in controlling electrical or photoelectric properties, at the same time as four halogen atoms into the layer when forming Oni's amorphous 1m(I). Therefore, in the present invention, it is used as a suitable raw material for introducing halogen atoms.

In order to structurally introduce hydrogen atoms into the amorphous layer (I) of O, in addition to the above, H2 or 5in4°812H6,
Silicon hydride gas such as 5isH8, 5i4H, etc.
Siliconization for total supply can also be performed by allowing the material to coexist with the deposition chamber and causing a total discharge.

For example, in the case of the reactive sputtering method, an S1 target is used, and a gas for introducing halogen atoms and H2 gas, including inert gases such as He and Ar as necessary, are introduced into the deposition chamber to form a plasma field ( By forming two surroundings and sputtering the S1 target, amorphous 'Jtl*(I) of O consisting of a-8i(H,X) is formed on the support.

Furthermore, doping of impurities is also performed and B21 (6
It is also possible to introduce a gas such as

In the present invention, the amount of electrons of hydrogen atoms (H) or the amount of halogen atoms (X) contained in the amorphous layer (I) of the light guiding material to be formed, or the amount of hydrogen atoms and halogen atoms The sum is usually 1 to 406 tomia%, preferably 5
It is desirable that the content be 30 atomic%.

In order to control the release of hydrogen atoms (H) and/or halogen atoms (X) contained in the amorphous layer (I), for example, the temperature of the support or the hydrogen atoms (H), Alternatively, the flow, discharge force, etc. of the starting material used for containing the halogen atoms (X) into the deposition system may be controlled.

In order to provide the layer region (v) containing O group V atoms and the layer region (0) containing oxygen atoms in the amorphous layer (I) of O, a glow discharge method or a reaction sputtering method (26) can be used. During the formation of the amorphous layer (I),
The starting material for the introduction of group V atoms and the starting material for the introduction of oxygen atoms are used together with the starting materials for forming the amorphous layer (I) described above, respectively. This is achieved by controlling the amount and containing it.

The layer region (0) containing oxygen atoms and the j-region containing O group atoms (0) constituting the amorphous layer (I) of O
When using the glow discharge method to form V) respectively, ft%
The starting materials that become the raw material gas for forming the I-region are:
The above-mentioned starting materials for forming the amorphous 1@(I) are selected according to point 1, and the starting materials for introducing oxygen atoms and/or the starting materials for introducing V group atoms are selected from Added.

As such a starting material for introducing an oxygen atom or a starting material for introducing an O-V group atom, a gaseous substance or a gasifiable substance containing at least an oxygen atom or an O-V group atom may be used. Most of them can be used.

For example, if layer region (0) is to be formed, a raw material gas containing 7s(27) silicon atoms (Sl), a raw material gas containing oxygen atoms (0), and hydrogen as necessary. The atom CH)'')l is used by mixing / and a raw material gas whose constituent atoms are no-rogen atoms (X) at a desired mixing ratio, or it is used as a silicon atom (Si). The raw material gas and the raw material gas whose constituent atoms are oxygen atoms (0) and hydrogen atoms (H) are also mixed at a desired mixed negative ratio, or the constituent atoms are silicon atoms (Sl). Raw material gas, silicon atoms (Si), oxygen atoms (0
) and a raw material gas containing six hydrogen atoms (H) can be used in combination.

Alternatively, a raw material gas containing oxygen atoms (0) as constituent atoms may be mixed with a raw material gas containing silicon atoms (Sl) and hydrogen atoms (fH) as all constituent atoms.

Specifically, starting materials for introducing oxygen atoms include, for example, oxygen (02), ozone (03), and -11 nitrogen oxide 0C! Nitrogen oxide ("2) in l, -nitrogen dioxide (i2
o), nitrogen sesquioxide (N203), nitrogen tetroxide (28
) (N204) 1. i2lfi chloride (IJ205)
, nitrogen trioxide (NO,), silicon atom (Sl), oxygen atom (0), hydrogen atom fH) and all constituent atoms, for example, Schiffoxane (H,5iostH5), trisiloxane (H,5iO8iH20Sikls) etc. low grade 70
Kisan etc. can be mentioned.

When forming the layer region (V) using the glow spiral method, the starting materials for introducing O-V group atoms that are effectively used in the present invention are PH, PH,
, hydrogen north neighbor such as P2H4, PH4I, PF, , PF5
．． POl, , POl5. PBr, , PBr3. Examples include those with a halogen ratio such as P-type 3. In addition, AsH,...
AaF, .

As0J, , AsBr, , AaF5. SbH
3, St+IP, , SbF5. BbOJ, ,
81) OJ51BI Hs T B i CJs +
B i B rs and the like can also be mentioned as effective starting materials for introducing O-V group atoms.

The content of the O-V group atoms introduced into the layer region (V) containing the O-V group atoms is determined by the gas flow rate of the starting material for introducing the O-V group atoms introduced into the deposition chamber, the gas flow ratio, It can be arbitrarily controlled by controlling discharge power, support temperature, pressure inside the deposition chamber, etc.

(29) To form the layer region (0) containing all oxygen atoms by sputtering, target a single crystal or polycrystalline 81 Quafer or 8102 wafer, or a wafer containing a mixture of Sl and 5102. This may be done by sputtering in a gas atmosphere.

For example, if a Si wafer is used as a target, the raw material gas for introducing oxygen atoms and optionally hydrogen atoms and/or halogen atoms is diluted with a diluent gas as necessary to create a sputtering target. The 81 Quahar may be sputtered by introducing the gas into a deposition chamber and forming a gas plasma of these gases.

Also, separately, sl and 8102 are separate targets, and by using a single mixed target of sl and 8102, hydrogen atoms are at least CH ) or/and by sputtering (30) in a gas atmosphere containing halogen atoms (X) as constituent atoms.

As the raw material gas for introducing oxygen atoms, the raw material gas for introducing oxygen atoms among the raw material gases shown in the glow discharge example described above can be used as an effective gas for sputtering as well.

In the present invention, the diluent gas used when forming the O amorphous layer (I) by the glow delta radiation method, or the sputtering used when forming the O amorphous layer (I) by the 01 sputtering method. As the gas for use, Tokoura rare gas such as He, Ne
, Ar, etc. can be mentioned as suitable ones.

In the photoconductive member of the present invention, the layer region (B) not containing group O-V atoms is provided on the layer region (V) containing group O-V atoms (layer region (B) in FIG. 1). 105) contains a substance that controls the conduction characteristics, so that the conduction characteristics of the layer region (B) can be arbitrarily controlled as desired.

Such substances include so-called impurities in the field of conductors, and in the present invention (61), a-8 constituting the amorphous layer (I) to be formed is used.
A P-type impurity that gives L(H,
group atoms), such as B (boron), AJ (aluminum), Ga (gallium), In (indium), TJ (
thallium), etc., and particularly preferably used are B,
It is Ga.

In the present invention, the content of the substance that controls the conductive properties contained in the layer region (B) is determined by the conductive properties required for the layer region (B) or the substance that is in direct contact with the layer region (B). It can be selected ubiquitously based on the organic relationship, such as the characteristics of other 1-regions provided as a lumbosacral region and the relationship with the characteristics at the contact interface with the lumbosacral layer region.

In the present invention, the content of the substance controlling the conductive properties contained in the layer region (B) is usually 0.0
01 to 1000 ppm.

Preferably 0.05 to 500 atomic ppm,
The optimum content is 0.1 to 200 atomlc ppm.

(Substances that control conduction properties in the six-layer region (B), such as
In order to introduce the group atoms structurally, (at the time of @ formation, the starting material for introducing the group atoms is placed in a gaseous state in a deposition chamber, and other materials are used to form an amorphous layer (I) of O. It is sufficient to introduce it together with the starting material.

As a starting material for introducing such an O-group atom, 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, as a starting material for introducing boron atoms, B2H61B4HIOI is used as a starting material for introducing boron atoms.
B5H9TB5H++ IB6H,. l Ba HI3
1 Bj Boron hydride such as HI3, BP, , BCl
Examples include boron halides such as 2°BBr3. In addition, AJOJ, , (3aQ15. Ba(OH,
), , IQOノ5. Tno07. etc. can also be mentioned.

In the photoconductive member 100 shown in FIG. The purpose of the present invention is achieved in terms of moisture resistance, continuous repeated use characteristics, pressure resistance, use environment characteristics, and durability.

In the present invention, each of the amorphous materials forming the O amorphous layer (1) and the O amorphous layer (n) has a common constituent element of silicon atoms. , chemical stability is sufficiently ensured at the laminated interface.

The amorphous layer (n) of Oni is an amorphous material (a-81zO1-z) composed of silicon atoms and carbon atoms.

hand·· However, o<x<i)A is formed.

Oni's amorphous I@(I
[) 106 is formed by a sputtering method, an ion inflation method, an ion blating method, an electron beam method, or the like. The manufacturing method for these is
The method is 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 produced, but photoconductive materials having the desired characteristics are manufactured. It is relatively easy to control the manufacturing conditions for the amorphous layer (n
) The sputtering method, the electron beam method, or the ion blating method is preferably employed because of the advantages such as ease of introduction into the interior (64).

Oni amorphous 1-(n') by sputtering method
K to form a target is a wafer containing a mixture of single crystal or polycrystalline S1 quafer and C wafer, or a mixture of 81 and 0, and is spun and tarned in a clear gas atmosphere. This can be done by doing.

For example, when using an S1 wafer and a C wafer as targets, a sputtering gas such as Hθ, Ne, Ar, etc. is introduced into a deposition chamber for sputtering to form a gas plasma, and the S1 wafer and C wafer are used as targets. C
Just sputter the wafer.

Another method is to use a single target containing a mixture of SL and C, introduce a sputtering gas into the apparatus system, and perform sputtering in the gas atmosphere. In the case where the electron beam method is used (in six or two vapor deposition boats, single crystal or polycrystalline high purity 7 recon and high purity graphite are placed in each, and each is independently co-deposited by an electron beam, or Silicon and graphite may be deposited at a desired mixing ratio in the same deposition boat using a single electron beam.
In the former case, the content ratio of silicon atoms and carbon atoms is controlled by changing the applied pressure of the electron beam to silicon and graphite, and in the latter case,
This is controlled by determining the mixture t of silicon and graphite in advance. When using the ion blating method, various gases are introduced into the evaporation tank and a high frequency electric field is applied to the coils scattered around the tank in advance to produce a ``C glow'', and the electron beam method is used to perform All you have to do is evaporate it.

The amorphous layer (II) in the present invention is
) are carefully formed to provide the required properties as desired.

(66) In other words, materials whose constituent atoms are SL and O can have forms ranging from crystalline to amorphous depending on the conditions of their creation, and physical properties ranging from conductive to semiconductive to insulating. In the present invention, a-8140+- which has characteristics 1 depending on the purpose is used. X
The formation conditions are strictly selected according to the desired conditions so that the formation of the .

For example, in order to provide an amorphous layer (II) with the main purpose of improving pressure resistance, a-stxO+-x is created as an amorphous material with remarkable insulating behavior in the usage environment. be done.

However, when the amorphous layer (II) 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 is relaxed to some extent, and it becomes more resistant to the irradiated light. a-stxa,-1 is created as an amorphous material having a certain degree of sensitivity.

When forming the amorphous amorphous layer (II) consisting of a-stxcl-:c (37) on the surface of the amorphous layer (I) of the In the present invention, the temperature of the support during layer formation is an important factor that influences the structure and properties of 1-, and in the present invention, the temperature of the support during layer formation is It is desirable that the

In order to effectively achieve the purpose of the present invention, the temperature of the support when forming the amorphous layer (II) should be adjusted according to the method for forming the amorphous layer (II). Formation of the amorphous layer (II) is performed by appropriately selecting an optimum range, preferably from 20 to 300C, most preferably from 20 to 250C.
It is desirable that this is the case.

To form Oni's amorphous layer ([), sputtering is used because it is relatively easy to delicately control the composition ratio of the atoms that make up the layer and to control the layer thickness compared to other methods. It is advantageous to adopt the method and electron beam method, but when forming Oni's amorphous 1@(n) using these layer forming methods, the temperature during layer formation as well as the support temperature described above must be adjusted. Created by discharge power (
38) It can be cited as one of the important factors that influences the properties of a-slXcl-1.

a- having the characteristics for achieving the object of the present invention;
The discharge power conditions for effectively creating slxa and -X with good productivity are Fi50w~250Ws.
jit4Kl' is preferably set at 180 W to 150 W.

In the present invention, the above-mentioned nine ranges are listed as the preferred numerical ranges of the support temperature and discharge power for creating the amorphous layer (II), but these layer creation factors is not determined independently and separately, but is based on the amorphous layer (
If) is formed, it is desirable that the optimum value of each creation factor be determined based on mutual organic relationships.

It of the carbon atoms contained in the amorphous layer (If) in the photoconductive member of the present invention is the amorphous layer (II) of the photoconductive member of the present invention.
Similar to the production conditions of the present invention, it is important to form a layer that provides the desired properties to achieve the objects of the present invention.

The ambiguity of carbon atoms contained in the amorphous layer (n) in the present invention is usually 1X10-5 to 90 atomic%, preferably 1 ~80 atomic %, optimally 10-75
It is desirable to set the value to atomic%.

That is, if it is expressed as a-81x01-x above, X is usually 0.1 to 0.99999, preferably 0.2 to 0.9.
9, optimally between 0.25 and 0.9.

The numerical range of the layer thickness of the amorphous layer (II) in the present invention is appropriately determined according to the new type according to the intended purpose so as to effectively achieve the purpose of the present invention.

In addition, the 1-thickness of the amorphous layer (II) of Oni is as follows: II (I
I) an amorphous layer of carbon atoms contained in
The relationship with the layer thickness in I) also needs to be appropriately determined as desired based on the organic relationship depending on the characteristics required for each layer region. 1. In addition, it is desirable to consider the economical aspects including productivity and mass production.

(40) The layer thickness of the amorphous layer (If) in the present invention is usually 0.003 to 30μ, preferably 0.004 to 30μ.
20μ, maximum M 匝Fi Q, 005
4i is preferable to be 10μ.

The support used in the present invention may be tetraelectric or electrically insulating. Examples of the conductive support include Nl0r, stainless steel, AJ, Or, Mo
, Au, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pa and alloys such as Tore.

As the insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene monochloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. Preferably, at least one surface of these insulating supports is conductively treated, and the other 1- is preferably provided on the conductively treated surface side.

For example, if it is glass, there is a titcr on its surface.
.

A71. , Or, MO, Au, Engr, IJb, Ta
, V, Ti, Pt, Pcl, Engineering (120s + S n
o21 (41) Conductivity is imparted by providing a thin film made of ITO (In2O, +SΩ02), or if it is a synthetic resin film such as polyester film, Ni0r, A
J, Ag, Pb, Zn, Ni, Au, Or, Mo, Ir
, Nb, Ta, V.

A thin film of a metal such as 'I'l, Pt, etc. is provided on the surface by deep evaporation, steron beam evaporation, sputtering, etc., or the surface is laminated with the metal, and tetraelectricity is imparted to the surface. Ru. 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.
If 0 is used as an image forming member for photocopying, it is desirable to use an endless belt or a cylindrical shape for 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. In such cases, from the viewpoint of manufacturing and handling of the support, mechanical strength, etc., the thickness is usually set to 10μ or more.

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

FIG. 11 shows an example of a photoconductive member manufacturing apparatus.

Gas cylinders 1102 to 1106 in the figure are sealed with raw material gases for forming each region 1 of the present invention. As an example, 11o2 is 5iH4 diluted with He (purity 99. 999%.

Hereinafter, it will be abbreviated as 5IH47Hθ. ) cylinder, 11o3 is He
PH, gas (purity 99.999%, hereinafter referred to as P) diluted with
H, /f (abbreviated as a) cylinder, 1104 /i Ar
fj, X (purity 99.99cm) cylinder, 1105
is a No gas (purity 99.999%) cylinder, and 1106 is diluted with H8 and EIIF4 dregs (purity 99.999%).
, hereinafter abbreviated as 5iIP4/He. ) It is a cylinder.

In order to flow these gases into the reaction chamber 11o1, pulps 1122 to 1126 of gas cylinders 1102 to 1106,
Check that the leak pulp 1155 is closed,
Father, inflow pulp 1112-1116, outflow pulp (43
) 1117 to 1121, after confirming that the auxiliary pulp 1162 is opened, first the main pulp 1134i is opened to exhaust the reaction chamber 1101 and gas pipe inner metal. Next, vacuum gauge 1
When the reading of 136 becomes approximately 5 X 10-' torr, the auxiliary pulp 1132 and the outflow pulps 1117 to 11
Close 21.

Next, an example will be given in which a photoconductive member having the layer structure shown in FIG. 1 is formed on the base 1167. s iH4/AE gas from gas cylinder 1102, gas cylinder 1103 Yosu PH
5/Hθ gas and uO gas from the gas cylinder 1105. Open the pulp 1122, 1125, 1125 and set the pressure on the outlet pressure gauges 1127, 1128, 1150 to 1 kg, respectively.
/cm2, and the inflow pulp 1112, 1113.1
115 gradually open each mass flow controller 11.
07.1108.1110 respectively. Subsequently, the outflow pulps 1117, 111B, 1120, and auxiliary pulp 1152 are gradually fought to release the respective gases into the reaction chamber 11.
01. SiH4/He gas flow t at this time
Outlet valve 1117.11 so that the ratio of PHs/He gas flow rate and No N gas flow rate is the desired value.
18. Adjust the opening of the main pulp 1134 while reading the vacuum gauge 1156 so that the (44) pressure in the reaction chamber reaches the desired value. Then, the temperature of the substrate 1137 is set to 1 power by the heating heater 1138 to cause glow awakening in the reaction chamber 1101, and at the same time, the
Control the distribution concentration in the thickness direction of oxygen atoms contained in the layer formed by gradually changing the flow rate of o gas manually or by using an externally driven motor or the like in the pulp 1120. When a layer region (PIO) containing phosphorus atoms and oxygen atoms is formed to a desired layer thickness, the outflow pulp 1118 and 1120 are closed, and the reaction chamber 1101 is filled with a layer containing no oxygen atoms and phosphorus atoms. The amorphous layer (I) having desired characteristics can be formed on the substrate 1137 (45) in this manner.

The layer region (V) containing phosphorus atoms is an amorphous layer of O (
In the formation process of I), PH, /HθH at an appropriate point
By cutting off the flow of e into the reaction chamber 1101, a desired layer thickness can be formed, and the layer region (V) becomes the layer region (
0) can be realized either in the case of occupying the entire layer area or in the case of occupying a part of the layer area. For example, in the above example, when the layer region (PIO) is formed to a desired layer thickness, the inflow of No gas into the reaction chamber 1101 is controlled by the outflow valve 1120.
By continuing to form the layer under the same conditions except for completely cutting it off by completely closing it, the layer region containing phosphorus atoms but not oxygen atoms on the layer region (PTO) becomes a layer region containing no oxygen atoms. It can be formed as part of the crystalline layer (I).

In addition, when forming a layer region that does not contain phosphorus atoms but contains oxygen atoms, for example, N.

The layer may be formed using gas and 51H4Ae gas.

When containing halogen atoms (46) in the amorphous layer (I) of O, the above gas is mixed with SiF4/H, for example.
e is added to the history and sent into the reaction chamber 1101.

To form an amorphous layer (I) of an amorphous layer (I), the amorphous layer (I) is formed using, for example, a chipping process. First, open '/Yatsuta 1142i. All gas supply nozzles are once closed, and the reaction chamber 1101 is evacuated by fully opening the main nozzle (J nozzle 1164).

On one pole 1141 to which high-pressure forming force is applied, a target is provided in advance in which a high-purity silicon oxide 142-1 and a high-purity graphite oxide 1142-2 are placed in a desired area ratio. From gas cylinder 1104,
Ar gas is introduced into the reaction chamber 1101 via VC, and the reaction chamber 11
Main valve 1154 is adjusted so that the internal pressure of 01 is 0.05 to 1 torr. By turning on the high pressure 1 source 1140 and sputtering the target, an amorphous layer (I) can be formed on the amorphous layer (I).

The carbon atoms contained in Oni's amorphous #(II) are determined by the sputtering area ratio of 7 Recon Cueno 11142-1 and graphite wafer 1142-2, and the target (47) cut 't-1'F formation. It can be controlled as desired by adjusting the mixing ratio of silico/powder and graphite powder as desired.

Needless to say, all outflow valves other than those for gases required when forming each layer are closed, and when forming each layer, the gas used to form the previous layer is inside the reaction chamber 1101 and the outflow valve 1117 is closed. In order to avoid remaining in the piping leading from ~ 1121 to the reaction chamber 1101, the outflow valves 1117 to 1121 are closed, the auxiliary valve 1132 is opened, and the main valve 1164 is fully opened to temporarily evacuate the system to a high vacuum. Perform as necessary.

Example 1 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen concentration distribution as shown in FIG. 12 in the first and second region layers was manufactured under the conditions shown in Table 1.

The image forming member thus obtained was placed in a charging exposure experimental apparatus, corona charging was performed at 05.0 V for 0.2 sea, and a light image was immediately irradiated. The light image uses a Tan (48) Gesten Lang light source, 1.5 Jux-se
The amount of light a was irradiated through a transmission type test chart.

Immediately thereafter, ■ by cassgating a charged developer (including toner and carrier) on the surface of the member,
A good toner image was obtained on the surface of the member. Toner image on the member Gold, transferred onto transfer paper with corona charging of 95.0, resulting in a clear, high-density image with excellent resolution and good gradation reproducibility! Obtained.

Example 2 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen distribution concentration as shown in FIG. 13 in the first and second layers was produced under the second condition.

Other conditions were the same as in Example 1.

Using the thus obtained image forming member, an image was formed on a transfer paper under the same conditions and procedures as in Example 1, and an extremely clear image quality was obtained.

Example 6 Using the manufacturing apparatus shown in FIG. 11, an image forming member having an oxygen distribution concentration as shown in FIG. 5 in the first layer (49) was produced under the conditions shown in Table 3.

Other conditions were the same as in Example 1.

When an image was formed on a transfer paper using the image forming member thus obtained under the same conditions and procedures as in Example 1, an extremely clear image quality was obtained.

Example 4 During the formation of amorphous 1i (II) -7 Recon Ueno・
By changing the area ratio of graphite and
n) An image forming member was prepared in exactly the same manner as in Example 6 except that the content ratio of silicon atoms to carbon atoms therein was changed.

The image forming member thus obtained was subjected to the image forming, developing and cleaning steps as described in Example 1 about 50,000 times, and then image evaluation was performed, and the results shown in Table 4 were obtained.

Example 5 An image forming member was produced in the same manner as in Example 1 except that the thickness of the amorphous layer (n) was changed. The image forming, developing, and (50) leaning steps as described in Example 1 were repeated to obtain the results shown in Table 5.

1-Formation was carried out in the same manner as in Example 1 except that
When image quality was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 6.

Electrophotographic image forming members were prepared in accordance with the conditions and procedures shown in Examples 1 and 2, except that the forming conditions were as shown in Table 7, and evaluated in the same manner as in Example 1. As a result, good results were obtained for each of them, particularly in terms of image quality and durability.

Table 5 (56) (5-υ-1 (57 no 2

[Brief explanation of the drawing]

FIG. 1 is a schematic J-configuration diagram for explaining the layer structure of the light guide member of the present invention, and FIGS. 2 to 10 respectively show layer regions containing oxygen atoms constituting an amorphous layer. FIG. 11 is an explanatory diagram for explaining the distribution state of oxygen atoms in (0), and FIG. 11 is a schematic explanatory diagram of the apparatus t used in the present invention, and FIGS. FIG. 3 is an explanatory diagram showing the distribution state of oxygen atoms in an example. DESCRIPTION OF SYMBOLS 100... Light guide member 101... Support body 102... O's amorphous layer (I) 103... First layer region (0) 104... Second 1 m region (V) 105... Upper 1fi region 106... Oni amorphous layer (It) 107... Free surface applicant Canon Corporation lθO □ C □C □ O C □C □C 1 rin (1 4p + 11.P, ＼ Continued from page 1 0 Inventor Shigeru Shirai Canon Co., Ltd., 3-30-2 Shimomaruko, Ota-ku, Tokyo

Claims (1)

[Claims] (1) A support for a photoconductive member, an amorphous layer of photoconductive material composed of an amorphous material having silicon atoms as a matrix, and an amorphous layer containing silicon atoms and carbon atoms. and an amorphous layer made of an amorphous material, in which the constituent atoms a first layer region containing an oxygen atom as a constituent atom; and a second layer region containing an atom belonging to group O of the periodic table as a constituent atom; 1. A photoconductive member, characterized in that the photoconductive member is included in the support layer.