JPS61262745A - Photoconductive member - Google Patents

Abstract

PURPOSE:To obtain a photoconductive member remarkably high in photodegradation resistance, capable of being used repeated for a long period, and hardly measurable in residual potential by forming an amorphous layer contg. O or O and N, and having specified characteristics. CONSTITUTION:The photoconductive member 1 is constituted by forming the amorphous layer 3 contg. O or O and N, and having photoconductive characteristics: a dark conductivity of 10<-15>-10<-11>(OMEGA.cm)<-1>, a photoconductivity of 10<-9>-10<-6>(OMEGA.cm)<-1> when light is incident in an intensity of 100mW/cm<2>, an optical band gap of 1.9-2.5eV, and a photoconductivity to dark conductivity ratio of 10<4>-10<6>, on a support 2, optionally conductive or insulating, and transparent or opaque, and in the case of a conductive substrate, for example, made of Al, stainless steel, NiCr, Cr, Mo, W, Au, Ta, Ti, Ni, Pt, or the like, or their alloy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photoconductive member, and more particularly to a photoconductive member in which a silicon-based amorphous layer having specific properties is provided on a support.

[Prior Art] Conventionally, inorganic materials such as Se and ZnO, and organic materials such as poly-N-vinylcarbazole and trinitrofluorenone have been used as photoconductive layer materials in photoconductive members such as electrophotographic image forming members and optical sensors. However, recently, amorphous silicon (hereinafter referred to as ra-siJ) has begun to attract attention. This is because photoconductive materials with a-8i photoconductive layers have properties similar to or better than conventional photoconductive materials, are harmless to humans and the environment, and are extremely durable. This is because it has advantages such as being large.

However, the conventional photoconductive member made of a-3i has poor electrical properties such as dark resistance, photosensitivity, and photoresponsivity.

For example, the reality is that sufficient optical and photoconductive properties have not yet been obtained.

When applied to electrophotographic image forming members and solid-state imaging devices,
Because a sufficient charging potential cannot be obtained, dark decay (dar
k decay) is extremely fast, making it difficult to apply normal electrophotography, and in a humid atmosphere, the above-mentioned tendency is so pronounced that in some cases, the charged potential cannot be maintained at all until the development time.

One of the ways to improve these points is (1) a-8.
Between a photoconductive layer consisting of i and a support supporting the photoconductive layer, carriers are prevented from flowing into the photoconductive layer from the support side and are generated in the leading ffi layer by irradiation with electromagnetic waves such as light. A photoconductive member has been proposed that has an intermediate layer that allows Chiaria moving toward the body to pass from the photoconductive layer side to the support side (Japanese Patent Laid-Open No. 57-5816
No. 1), the intermediate layer of this photoconductive member is composed of a non-photoconductive amorphous material based on silicon atoms and nitrogen atoms and containing halogen atoms, and has a thickness of 30 to 100 mm.
There were about 0 people.

This photoconductive member maintains the charged potential by the high resistivity of the intermediate layer, but since the thickness of the intermediate layer is extremely thin (30 to 1,000 layers) as mentioned above, this intermediate layer is formed on a support. It is difficult to form uniformly over the entire support due to scratches, unevenness, etc. on the support surface.
If the toner is formed non-uniformly, the charging potential becomes extremely non-uniform and a good image cannot be formed. If a pinhole occurs, problems such as white spots will occur in that area. Also, if the intermediate layer is formed thickly to improve the charging potential over the entire band, the band ff1f! 1st place will improve, but
11! Since the intermediate layer is non-photoconductive, light etc. It becomes difficult to allow carriers generated in the photoconductive layer by magnetic wave irradiation and move toward the support to pass from the photoconductive layer to the support, resulting in a decrease in photoconductive properties and a large residual potential. It has the following disadvantages.

Another example of improving the photo-R electrical characteristics is:
(2) Oxygen atoms are added as impurities to the photoconductive layer consisting of a-Sl so that they are less on the support side and more on the surface side (
In other words, the a-S is contained non-uniformly in the thickness direction.
A photoconductive member has been proposed that aims to improve the band Wi potential by increasing the resistance of the i-based photoconductive layer (Japanese Unexamined Patent Publication No. 57-1
15553).

According to this photoconductive member, it is possible to maintain a charged potential in the photoconductive layer itself without providing a special layer between the photoconductive layer and the support as in (1) above. However, this photoconductive member gives priority to the function of holding the IF electric potential, and the photoconductive member gives priority to the function of holding the IF electric potential. Increasing the content of acid Li4 atoms in the electrolytic layer has the disadvantage that the photosensitivity decreases, and in order to obtain practical photosensitivity, the function of holding the charged potential must be sacrificed to some extent.

In addition, in the production of this photoconductive member (mentioned in item 2), the light guide 1tjl! In order to contain oxygen atoms in l, acid 1(0,
), ozone (O, ), etc. are used.

In fact, S I Ha etc. were decomposed by the glow discharge method and a −
The characteristics of the photoconductive layer when oxygen (0,) is used to contain oxygen atoms when forming the photoconductive layer 111 of No. 81 are shown in FIGS. 4 and 5.

Figure 4 shows the relationship between the mixing ratio of oxygen (O3) in silane (SiH4) and the optical band gap of the formed photoconductive layer. There is a problem in increasing the resistance because the optical bandgap does not widen. Figure 5 shows the relationship between the mixing ratio of oxygen (02) in silane (SiH4) and the photoelectricity of the formed light-guiding ffi layer. However, when the mixing ratio of oxygen (0,) increases, the dark conductivity decreases to some extent, but ΔM1100+IIW/c
There is a problem in that the photoconductivity of J when light is incident thereon suddenly decreases, resulting in a decrease in photoconductive properties.

Furthermore, when oxygen (0,) is mixed into silane (SiH4), the silane (SiH,) reacts instantaneously with the mixed oxygen (0,) before being decomposed by glow discharge, resulting in a photoconductive layer. It is difficult to efficiently incorporate oxygen atoms into the photoconductive layer, and the equipment for forming the photoconductive layer requires complicated equipment to ensure homogeneous oxygen content, making it difficult to mass-produce. has been done.

However, it is conceivable to add some of the measures in (1) to (2) above with the intention of improving the charging potential characteristics without reducing the photosensitivity, but the above-mentioned problem still remains. However, the current situation is that it is not possible to obtain a-5i-based photoconductivity that fully satisfies the electrical, optical, and photoconductive properties of charging potential characteristics, photosensitivity, and photoresponse characteristics. be.

[Purpose] The purpose of the present invention is to have electrical, optical, and photoconductive properties that are stable at all times, to be hardly limited by the usage environment, to be resistant to light deterioration, to be able to be used repeatedly, and to have no or almost no residual potential. It is an object of the present invention to provide a photoconductive member that is not

Another object of the invention is in the entire visible light range.

It is an object of the present invention to provide a photoconductive member that has high photosensitivity, can change the photosensitivity depending on the wavelength of light, and has fast photoresponse characteristics.

Another object of the present invention is to have a sufficient charge retention function during charging processing for electrostatic image formation to the extent that general electrophotography can be applied very effectively when applied to electrophotography. It is an object of the present invention to provide a photoconductive member which has excellent electrophotographic properties with almost no deterioration in its properties even in a humid atmosphere.

Still another object of the present invention is to provide a photoconductive member useful for electrophotography, which can easily consistently obtain high-quality images with high density, excellent gradation, and high resolution. be.

Another object of the present invention is to provide a photoconductive member that can be manufactured by a method with excellent mass productivity without using complicated means.

[Structure] The present invention provides a photoconductive member in which an amorphous layer having silicon atoms as a base material is provided on a support, the amorphous layer containing oxygen atoms or oxygen atoms and nitrogen atoms, 10-”
It has a dark conductivity in the range of ~10-'' (Ωc+a)-1, and when light is incident at AM1100mW/cd, it has a dark conductivity of 1.
It has a photoconductivity in the range of O-6 to io-'(0cm)-1, an optical band gap in the range of 1.9 to 2.5eV, and the photoconductivity and dark conductivity as described above. The ratio of
It is characterized by having photoconductive properties in the range of 4 to 106.

Incidentally, the inventors of the present invention have conducted various studies and examinations to achieve the above object, and have found that if the above-mentioned specific properties are imparted to the amorphous layer, good electrical, optical, and photoconductive properties can be obtained. It has been confirmed that this can be obtained, and the present invention has been completed based on this knowledge.

The present invention will be explained in more detail below without referring to the drawings. FIG. 1 shows that a photoconductive member 1 according to the present invention has a structure in which an amorphous layer 3 is provided on a support 2. 4 indicates a free surface.

As mentioned above, the amorphous layer 3 contains oxygen atoms or oxygen atoms and nitrogen atoms, and has a range of 1o −11 to 10 −+E (
AM1100■W with dark conductivity in the range of Ωam)-1
/cd light incidence, 1O-6~10-'(Ωc
It has a photoconductivity in the range +s)-' and an optical bandgap in the range 1.9-2.5 eV.

and the ratio of the photoconductivity to the dark conductivity is 104 to 1.
It has photoconductive properties in the range of 0@.

The support 2 may be conductive or electrically insulating, transparent or opaque, and examples of the 1° conductive support include AQ-stainless steel and NiC.
r, Cr, Mo, W, Au, Ta-Ti
, Ni, Pt, or alloys thereof can be used.

Alternatively, it may be a laminate of these metals.

Also, carbon or carbon-based alloys can be used.

The electrically insulating support may be a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, polyimide, acetate, polypropylene, polyvinyl chloride, Teflon, or a laminate thereof.

Other transparent materials such as glass, ceramic, and paper can be used. These electrically insulating supports usually have one surface conductively treated, and an amorphous layer 3 is formed on the conductively treated surface side. For example, in the case of glass, conductive treatment is performed by providing a thin film of the metal or alloy thereof as the conductive support material on its surface. To form a thin film, it is formed on its surface by conventional vacuum evaporation, electron beam evaporation, sputtering, plating, etc. In addition, r T which is a transparent conductive material
Conductive treatment may be performed by forming O (In202+SnO,) or SnO on the surface.

The support body 2 is formed into a cylindrical shape or a belt shape.

The shape, such as a plate shape, is determined depending on the use.

In the case of a high-speed continuous image forming member in this application example, an endless belt or a cylindrical shape is preferable.

The thickness of the support 2 is determined so that the desired amorphous layer 3 is formed, but in this application example, it may be within a range that allows its function to be sufficiently exhibited. In particular, from the viewpoint of manufacturing and handling, mechanical strength, and durability, it is usually sufficient if the thickness is 10 μm or more.

When the present invention is applied to an electrophotographic image forming member, the amorphous layer 3 formed on the support 2 and having silicon atoms as a base material is formed on the support 2 to effectively achieve the purpose. It is formed to have the following semiconductor characteristics.

■Amorphous material whose base material is p-type silicon: Amorphous material that contains only acceptors or amorphous material that contains both donors and acceptors and has a high density of acceptors as its base material.

■Amorphous with n-type silicon as the base material: Amorphous with silicon as the base material containing only donors or containing both acceptors and donors with a high donor density.

■Amorphous whose base material is l-type silicon...Amorphous whose base material is silicon where the donor or acceptor density is almost zero or the donor and acceptor density is the same.

Further, when the amorphous layer 3 whose base material is silicon contains either hydrogen atoms, deuterium atoms, or halogen atoms, and this amorphous layer 3 is formed by, for example, a glow discharge method,
Specifically, the halogen atoms are fluorine (F), chlorine ((d), bromine ( Br), iodine (I
), and particularly preferred are fluorine (F) and chlorine (CCU). The amorphous layer 3 can be formed by, for example, a vacuum deposition method that utilizes a discharge phenomenon such as a glow discharge method, a sputtering method, or an ion blating method.

For example, to form the amorphous layer 3 by the glow discharge method, carbon dioxide (CO2) or carbon dioxide (Cod) and nitrogen (N,
Gas, if necessary, raw material gas for introducing hydrogen atoms, deuterium atoms, or halogen atoms, and further, if necessary, doping gas containing group II or group V impurities that determine semiconductor characteristics can be reduced in pressure inside. is introduced into the deposition chamber to generate a glow discharge within the deposition chamber.

What is necessary is to form it on the surface of a predetermined support body that is placed in advance at a predetermined position and maintained at a predetermined temperature.

In the case of forming by sputtering method.

For example, when sputtering a target made of silicon in an atmosphere of an inert gas such as Ar or Ha or a mixed gas based on these inert gases, carbon dioxide (COt) or carbon dioxide (CO,) and nitrogen gas (N
2), and further introduce a raw material gas for introducing hydrogen atoms, deuterium atoms, or halogen atoms into a deposition chamber for sputtering, and deposit the material on a predetermined support surface that has been placed in a predetermined position and maintained at a predetermined temperature. It is better to form it on top.

SiH4g 81. is used as a silicon raw material gas when forming the amorphous layer 3 whose base material is silicon.
Ha e S1m Ha * S14 Hydrogenated silicon (silanes) that can be gasified or gasified, such as Ha, can be effectively used, and S1 is particularly effective in terms of workability in layer creation, ease of handling, etc. Preferred examples include iH4 and S it Hs.

Other effective silicon raw materials used in forming the amorphous layer 3 include silicon compounds containing silicon atoms and deuterium atoms that are in a gaseous state or can be gasified. For example 5iD4e
Examples include Sit Da and the like. Another example is gas state 5i2H, which has silicon atoms and halogen atoms as constituent elements. In addition, silicon compounds containing halogens that are in a gaseous state or can be gasified and have silicon atoms and halogen atoms as constituent elements may also be mentioned.For example, SiF,
Examples include Si, F, 5icQ, #S iB r a, and the like.

Hydrogen (H
), deuterium (D2) or halogen compounds such as fluorine, chlorine, bromine, iodine, BrF, C1
l F, CQF,.

Examples include interhalogen compounds such as BrF.

Each gas may be used not only individually but also in a mixture of multiple types at a predetermined mixing ratio depending on the purpose of a predetermined electrophotographic image forming member.

When forming the amorphous layer 3 by the ion blating method, polycrystalline silicon or single crystal silicon is placed in an evaporation boat as an evaporation source, and the silicon is heated by resistance heating or an electron beam method. After evaporation, the evaporated silicon can be passed through a predetermined gas plasma atmosphere and formed on the surface of a predetermined support that has been placed in a predetermined position and maintained at a predetermined temperature.

When forming the gas plasma atmosphere, carbon dioxide (
This can be achieved by introducing a source gas (CO2) and forming a gas plasma atmosphere.

FIG. 2 shows the relationship between the optical bandgap and the ratio of carbon dioxide (Co□) mixed into silane (SiH) in the photoconductive layer of the photoconductive member formed according to the above manufacturing example. The optical bandgap increases almost linearly as the proportion of carbon dioxide (CO2) mixed increases.

FIG. 3 shows the relationship between the electrical conductivity and the ratio of carbon dioxide (CO,) mixed into silane (SiH4) of the photoconductive layer of the photoconductive member formed according to the above manufacturing example. As the mixing ratio of carbon dioxide increases, the dark conductivity increases to 1o-t4
(Ωam)-', but AMI 100W/c
The photoconductivity of I# when light is incident is on the order of 10-'' (0 cm), indicating that it has very high photosensitivity with a ratio of photoconductivity to dark conductivity in the range of 10s to 106. .

As can be inferred from these Figures 2 and 3.

The photoconductive member of the present invention has electrical properties and optical properties.

All of the photoconductive properties are excellent.

By the way, in order to more effectively achieve the purpose of using the photoconductive member of the present invention for electrophotography, the electrical, optical, and photoconductive properties may be changed in the thickness direction. When forming the amorphous layer 3 by the glow discharge method, sputtering method, or ion blating method, the mixing ratio of the millicon raw material gases of carbon dioxide (CO,) or carbon dioxide (Co□) and nitrogen (N2) is controlled. This can be achieved by adjusting it in accordance with the growth of the crystalline layer 3.

6 to 8 show examples of application in which the optical bandgap of the amorphous layer 3 is varied in the thickness direction for various purposes as an electrophotographic image forming member.

In the figure, the horizontal axis indicates the distribution of the optical bandgap A at any position in the layer direction of the amorphous layer 3, indicating that the optical bandgap increases in the direction of the arrow. The vertical axis indicates the layer thickness of the amorphous layer 3, 10 indicates the interface position between the support 2 and the amorphous layer 3, and t indicates the surface interface position of the amorphous layer 3 on the free surface 4 side. This shows that the layer thickness t of the amorphous layer 3 increases from 1o to t.

In the example shown in FIG. 6, the distribution state of the optical band gap A of the amorphous layer 3 in the layer direction is from the interface position t0 between the support 2 and the amorphous layer 3 to the surface interface position fists. It is configured to have a band gap A, and a photoconductive member with such a configuration can further improve charging potential characteristics used when sensitivity on the short wavelength side is required as photosensitivity.

In the example shown in FIG. 7, the distribution state of the optical band gap A of the amorphous layer 3 in the layer direction is maximum at the surface interface position t, and more specifically at the interface position t between the support 2 and the amorphous layer 3. It is configured to have an optical band gap A, and a photoconductive member with such a configuration can effectively prevent carriers from flowing into the amorphous layer 3 from the support 2 side, and reduce the charging potential. can be further improved.

In the example shown in FIG. 8, the surface interface position t1 from the intermediate region of the amorphous layer 3 and the interface position t between the support 2 and the amorphous layer 3
. It is constructed so that the optical bandgap is large at the surface position t.

Even if the optical band gap of the interface position tll between the support body 2 and the amorphous layer 3 is the same, it may be a stationery, and it is arbitrarily determined depending on the purpose of use. The photoconductive member having such a configuration controls the photosensitivity on the short wavelength side by increasing the optical band gap at the surface interface position t1, and also controls the photosensitivity on the short wavelength side by increasing the optical band gap at the surface interface position t1, and also at the interface position t between the support 2 and the amorphous layer 3. By increasing the optical bandgap of the amorphous layer 3, it is possible to effectively prevent carriers from flowing into the amorphous layer 3 from the support 2 side, thereby further improving the charging potential. In these FIGS. 6, 7, and 8, the distribution of the optical band gap in the layer thickness direction has been explained.
is in the range of 1.9 to 2.5 eV in the entire amorphous layer 3, and is in the range of 10-1'' to 10-1!i(Ωa
m) has a dark conductivity in the range of
10-6 to 10-' (Ωc
It has a photoconductivity in the range of +a)-' and a photoconductivity in which the ratio of the photoconductivity to the dark conductivity is in the range of 104 to 104.

The amount of oxygen atoms contained in the amorphous layer 3 of the photoconductive member is
The optical band gap is selected to be in the range of 1.9 to 2.5 QV, preferably 0.5 to 70 at, omi
c%, preferably selected from the range of 1.0-70-70ajo%.

Carbon dioxide (CO,
It is desirable that the amount of oxygen atoms contained in the amorphous layer 3 formed when nitrogen (N) and nitrogen (N, ) are used is selected from the above range.

At the same time, nitrogen atoms are also contained in the amorphous J13, but are limited to values that do not deviate from the above-specified ranges of electrical, optical, and photoconductive properties.

The amount of hydrogen atoms, deuterium atoms, or halogen atoms contained as necessary in the amorphous layer 3 of the photoconductive member is usually 1 to 40a.
It is preferable to set it as 10 mic%, suitably 4-30a10-mic%. To determine the amount of hydrogen atoms, deuterium atoms, or halogen atoms contained in the amorphous layer 3, for example, the holding temperature of the support, the proportion of each raw material gas introduced into the vacuum deposition chamber, the discharge power, etc. are controlled. Just do it.

To control the semiconductor properties of the amorphous layer 3 of the photoconductive member,
Amorphous layer 3 is formed by glow discharge method, sputtering method, etc.
This is done by adding an n-type impurity, a p-type impurity, or an M-type impurity in a gaseous state to each raw material gas when forming the impurity, and controlling the amount thereof. To make the amorphous layer have an i-type or p-type tendency, use an element of group A of the periodic table, such as B.

Preferred examples include AQ, Ga, In, Tl1, and the like. For the n-type tendency, elements of group V A of the periodic table, such as P, Ass sb, B i, etc., are suitable. In order to contain such elements in the amorphous layer 3, hydrogen compounds or halogen compounds of each element, such as B2H, are used when forming the amorphous layer 3 by a glow discharge method or the like.

P Ha e At Ha −Bx Fe , P F2
This can be done by introducing a gas such as into a vacuum deposition chamber.

The amount of the element introduced into the amorphous layer 3 in order to have the desired conductivity type of the semiconductor properties of the amorphous layer 3 is 3×10−” a10+sic in the case of an element of group Ⅰ A in the synchronizer table. %
It is sufficient to dope within the following amount range, and in the case of elements in group A of the synchronous table, "5 XIO-' a10n
Doping may be done within the range of +ic% or less.

The thickness of the amorphous layer 3 of the photoconductive member in the present invention is determined as desired so that carriers generated in the amorphous layer are efficiently transported in a predetermined direction. When applied as an electrophotographic image forming member, the thickness is usually 3 to 100 μm, preferably 5 to 60 μm. When applied to optical sensors etc., it is usually 0.3 to 3 μm, preferably 0.5 to 1.5 μm.
Next, an example will be shown.

Example 1 A photoconductive member was produced using the apparatus shown in FIG. 9 according to the following operating procedure.

Substrate 6 with ITO vapor-deposited on a 1mm thick 3c+5x5c square glass plate with a cleaned surface, II with a cleaned surface
A substrate 7 with Cr deposited on a glass plate of III+ thickness of 3 cm + × 5 cm + square, and an AQ plate substrate 8 of 3 × thickness of 3 cm × 5 cm square whose surface has been polished and cleaned were placed in a glow discharge reduced pressure deposition chamber (hereinafter referred to as "chamber"). It was firmly fixed to the base body fixing member 9 at a predetermined position in the body 5.

The substrates 6, 7, and 8 are maintained at a predetermined temperature by a heater 10 within the substrate fixing member 9 with an accuracy of ±0.5° C. or less. The temperature is measured and controlled by a thermocouple (not shown). The base fixing member 9 is rotated by a motor 11.

Next, after all the valves in the system are closed, the vacuum exhaust valve 12 is opened, and after the chamber 5 is evacuated by a vacuum pump (not shown), the gas line introduction valve 52 is opened.
, outflow valve 13.14.16, inflow valve 25.26
．． 28 was opened, the gas line and mass flow controller 19, 20, and 22 were sufficiently evacuated to reduce the degree of vacuum in the chamber 5 to 5 X 10-" Torr or less. After that,
Heater power control bag! ! Turn on the switch 54 and apply current to the heating heater 10 to heat the substrate fixing member 9 and the substrates 6, 7, and 8 fixed to the surface thereof to 250°C.
The temperature was controlled at a constant temperature.

Then, the gas line inlet valve 52. Outflow valve 13
．． 14. , 16. After closing the inlet valves 25, 26, 28, the H2 gas cylinder 31. S i H, gas cylinder 34
, and carbon dioxide (hereinafter referred to as Co2) cylinder 4o, and after adjusting the pressure of the outlet pressure gauges 33, 36 and 42 by 1 kg/fiK, open the inlet valve 52. The outflow valves 13, 14 and 16 were opened, and the inlet valves 25, 26 and 28 were gradually opened to allow gas to flow into the mass blow controllers 19, 20 and 22. At this time, the mass flow controller controls the flow rate ratio of H, gas, Si Ha gas, and CO2 gas to Si
Add H4 gas 2 to 1/10 and add Co, /S i H4 to 5/
Adjusted to 1.

Next, while watching the pressure indication of the capacitance manometer 49 and adjusting the opening area of the vacuum exhaust valve 2 to control the exhaust volume, the pressure inside the chamber 5 is adjusted to L, 0T.
Adjust so that it becomes orr. After the pressure in the chamber 5 has stabilized, the switch of the high-frequency power source 50 is turned on and high-frequency power of 13.56 MH is supplied to the high-frequency electrode 51 to generate a glow discharge between the high-frequency electrode 51 and the substrate fixing member 9. let The input power density was 23 mW/cII.

The above conditions (substrate temperature 250°C, chamber pressure 1,
0 Torr, input power density 2.3 mW/cd) 1.
A photoconductive layer was formed by holding for 5 hours. Then high frequency power supply 5
After stopping the glow discharge by turning the switch 0 to the OFF state, the outflow valve 14.16 and the inflow valve 26.2
8 was closed to stop the supply of SiH4 gas, CO, and gas. Next, adjust the vacuum exhaust valve 12 to make the inside of the chamber 5 H,
After filling with gas only.

Turn off the switch of the heater power supply control device 54 and reduce the pressure in the chamber 5 to 0 Torr until the temperature of the substrate fixing member 9 and the bases 6, 7.8 becomes 100° C. or less.
It was held at r. Thereafter, the outflow valve 13 and inflow valve 25 are closed, firstly the inlet valve 52 is closed, and the vacuum exhaust valve 12 is fully opened to exhaust the inside of the chamber 5.
%Torr. Next, N2 gas is introduced into the chamber 5 using the leak valve 53 to bring the pressure to atmospheric pressure for the substrates 6, 7.
I took out 8. At this time, the thickness of the photoconductive layer formed was approximately 1.7 μm.

The electrical, optical, and photoconductive properties of the photoconductive member obtained by the above manufacturing method were measured by the following method.

An electrode was formed on the upper surface of the photoconductive layer of the substrates 6 and 7, and the dark conductivity and the photoconductivity when light was incident on A M 1100 mW/ad (71) were measured. Both conductive members have a dark conductivity of 3X10-" (Ωa
m)-1, the photoconductivity when light is incident on the photoconductive member using the substrate 6 from the glass substrate side is lXl0-"(Ωcm+
)-1 is obtained, and the ratio of photoconductivity to dark conductivity is 3.3.
A very good photoconductive layer was obtained with XIO'. Further, the optical band gap was 2.2 aV.

When the charging characteristics, dark decay, and photosensitivity of the photoconductive member using the substrate 8 were measured using a paper analyzer, sufficient characteristics were obtained that could be used as an electrophotographic image forming member.

Example 2 Similar to Example 1, a substrate 6 in which ITO was deposited on a glass plate
．． A substrate 7 and an AQ substrate 8 in which Cr was vapor-deposited on a glass plate were firmly fixed to a substrate fixing member 9 in the chamber 5. Next, after closing all the valves, the evacuation valve 12 was opened to evacuate the inside of the chamber 5 using a vacuum pump (not shown). Subsequently, the inlet valve 52, the outlet valve 14.16.1g, and the inlet valve 26.28.30 were opened to exhaust the gas line.

Next, the switch of the substrate heating control power source 54 is turned ON to supply current to the heating heater 10, the substrate fixing member 9, the base 6,
7.8 temperature was maintained at 250°C.

The temperature was measured with a thermocouple (not shown). Next motor 1
1 was rotated to rotate the substrate fixing member 9.

The inside of chamber 5 was evacuated to 5 x 10-'' Torr.

After that, all the valves in the glass line (inlet valve 52, outlet valve 14, 16, 18, inlet valve 26° 28, 3
0), and SiH4 gas cylinder 34, CO, gas cylinder 40. Argon gas (hereinafter referred to as A “gas”) cylinder 4
Open valve 35, 41, 47 of 6, outlet pressure gauge 3
6.42.48 The zero order inlet valve 52 and outlet valve 14.16 adjusted to have a pressure of 1 kg/c+#
．． After opening 18, the inlet valves 26, 28, and 30 were gradually opened to allow gas to flow into the mass flow controllers 20, 22, and 24. At this time, the flow rates of SiH, gas, CO, gas, and Ar gas were adjusted using a mass flow controller.

/Ar ratio is 1/4. The ratio of COw/S i H4 was set to 15/8.

Next, while observing the pressure indication of the capacitance manometer 49, the opening area of the evacuation valve 12 was changed to adjust the pressure inside the chamber 5 to 1.0 Torr. After the pressure inside the chamber 5 becomes stable at 1.0 Torr, the switch of the high-frequency power supply 50 is turned on to supply high-frequency power of 13.56 MH2 to the high-frequency electrode 51, and between the high-frequency electrode 51 and the substrate fixing member 9. generated a glow discharge.

The input power density was 47 mW/a#.

The above conditions (substrate temperature 250℃, chamber pressure, O
A photoconductive layer was formed by maintaining T'orr (input power density 47 mW/al) for 30 minutes. After that, after turning off the switch of the high frequency power supply 50 and stopping the glow discharge,
Outflow valves 14.16.18, Outflow valves 26, 28.
30 was closed, and the supply of SiH, gas, CO, gas, and Ar gas was stopped. Next, open the valve 32 of the H2 cylinder 31,
The outlet pressure gauge 33 was adjusted to be Ikg/aJ. Next, the outflow valve 13 and the inflow valve 25 are opened to introduce H2 gas into the chamber 5. After adjusting the evacuation valve 12 and filling the chamber 5 with H2 gas, the switch of the heater power supply control device 31 is opened. OFF and the temperature of the board fixing member 9 and the boards 6, 7.8 is 100℃.
The pressure inside the chamber 5 is kept at 1.0To until the temperature drops below ℃.
It was held at rr.

Then the outflow valve 13. The inflow valve 25 and the introduction valve 52 were closed, and the evacuation valve 12 was fully opened to exhaust the inside of the chamber 5 to 5 XIO-' Torr.

Next, Nt gas was introduced into the chamber 5 using the leak valve 53 to bring the pressure to atmospheric pressure, and the substrate 6°7.8 was taken out.

At this time, the thickness of the photoconductive layer formed was about 1.8 μm.

The electrical, optical, and photoconductive properties of the photoconductive member obtained by the above manufacturing method were measured by the following method.

AQ electrodes were formed on the upper surfaces of the photoconductive layers of the substrates 6 and 7, and the dark conductivity and the photoconductivity upon incidence of light of A M 1100 mW/al were measured. As a result, the dark conductivity of both photoconductive members using a substrate of 6°7 was 1×10-” (0 cm)-
", and the photoconductivity when light is incident on the photoconductive member using the substrate 6 from the glass plate side is 7.6X10-' (Ωam
)-1 is obtained, and the ratio of photoconductivity to dark conductivity is 7.6
A very good photoconductive layer of 104 was obtained. The optical bandgap was 2.0 OeV.

When the charging characteristics, dark decay, and photosensitivity of the photoconductive member using the substrate 8 were measured using a paper achierizer, sufficiently good characteristics were obtained to be applicable as an electrophotographic image forming member.

Example 3 A substrate 6 in which ITO was deposited on a glass plate in the same manner as in Example 1.
The substrate 7 with Cr deposited on a glass plate and the Afl substrate 8 are firmly fixed to the substrate fixing member 9 in the chamber 5. Next, after closing all the valves, the vacuum exhaust valve 12 is opened using a vacuum pump (not shown). It was exhausted. Subsequently, the introduction valve 52,
Outflow valve 14.16.17.1B, inflow valve 26.
28.29°30 was opened to exhaust the gas line. Next, the switch of the substrate heating control power supply 54 is turned on to apply current to the heating heater 10 and the substrate fixing member 9 and the substrate 6.7.
8 was heated and maintained at 250°C. The temperature was measured with a thermocouple (not shown). Next, the motor 11 was rotated, and the substrate fixing member 9 was rotated. Inside chamber 5 is 5 x 10-
' Exhausted to Torr.

After that, all valves of the gas line (inlet valve 52, outlet valve 14, 16, 17, 18, inlet valve 26, 28° 29, 30) were closed. Next, StH, cylinder 34, Co
2 gas cylinders 40. N2 gas cylinder 43. The valve 35.41.44.47 of the Ar gas cylinder 46 was opened to adjust the pressure of the outlet pressure gauge 36.42.45.4B to 1 kg/d.

Next, the introduction valve 52. Outflow valve 14.16.17゜1
After opening 8, gradually open inlet valve 26.2B, 29.30, mass plow controller 20.22.23
Gas was introduced at 24°C. At this time, SiH4 gas, CO, and gas are supplied from the first mass blower controller.

Adjust the flow rates of N2 gas and Ar gas.

The ratio of S t H4/A r is 1/4. CO* /
S i H4 ratio is 1/1. Go, /N, (71
The ratio was set to 2/1&::.

Next, while observing the pressure indication of the capacitance manometer 49, the opening area of the evacuation valve 12 was changed to adjust the pressure inside the chamber 5 to 1.0 Torr. After the pressure inside the chamber 5 stabilizes at 1.0 Torr, the switch of the high frequency power source 50 is turned on to supply high frequency power of 13.56 MH to the high frequency electrode 51, and the high frequency electrode 51 and the substrate fixing member 9 are connected to each other. A glow discharge was generated in between. The input power density at this time is 47+++W/aJ
And so.

The above conditions (substrate temperature 25Q'C, chamber pressure 1.
A photoconductive layer was formed by maintaining a temperature of 0 Torr and an input power density of 47 mW/aJ for 30 minutes. After that, after turning off the switch of the high frequency current 50 and stopping the glow discharge, the outflow valve 14.16.17.18 and the inflow valve 26.28
, 29. Close 30, S i Ha gas, CO, gas,
The supply of N2 gas and Ar gas was stopped. Next, when the valve 32 of the H gas cylinder 31 is opened, the outlet pressure gauge 33 is 1 kg.
I adjusted it so that it becomes /at. Subsequently, the outflow valve 13 and the inflow valve 25 were opened, and N2 gas was introduced into the chamber 5.

Next, after adjusting the vacuum exhaust valve 12 and filling the inside of the chamber 5 with N2 gas, the switch of the heater power supply control device 51 is turned off, and the substrate fixing member 9 and the substrates 6, 7 are turned off.
, 8 was maintained at 1.0 Torr until the temperature of the chamber 5 became 100° C. or lower. Then the outflow valve 13. Close the inflow valve 25 and introduction valve 52, fully open the vacuum exhaust valve 12, and vacuum the inside of the chamber 5 by 5X.
Exhausted to 10-”rorr. Next, leak valve 5
3, nitrogen gas was introduced into the chamber 5 to bring it to atmospheric pressure, and the substrates 6, 7.8 were taken out. The thickness of the photoconductive layer formed at this time was about 1.5 μm.

The electrical, optical and photoconductive properties of the photoconductive member obtained by the above manufacturing method were measured by the following method.

AQ on the top surface of the photoconductive layer of the photoconductive member using the substrates 6 and 7.
Form electrodes to increase dark conductivity and AML 100mW/
The photoconductivity at the time of light incidence of aJ was measured.

As a result, the dark conductivity of both the photoconductive members using substrates 6 and 7 was 5X10-14 (Ωcm) −', and the photoconductivity when light was incident on the photoconductive member using substrate 6 from the glass plate side was 5 ×1O-9(Ωcm)-1 was obtained.

A very good photoconductive layer was obtained with a ratio of photoconductivity to dark conductivity of 1X10', and an optical bandgap of 2.09 eV.

When the charging characteristics, dark decay, and photosensitivity of the photoconductive member using Substrate 8 were measured using a paper analyzer, sufficiently good characteristics were obtained to be applicable as an electrophotographic image forming member.

Example 4 Similar to Example 3, the AQ boards 6, 7.8 are fixed to the board fixing member 9.
was firmly fixed. The SL wafer was also fixed at the same position. The next operation was the same as in Example 3 to form a photoconductive source.

When the charging characteristics, dark attenuation, and photosensitivity of the obtained photoconductive member were measured using a paper analyzer, it was found that the properties were sufficiently good to be applicable as an electrophotographic image forming member, and at the same time, it was found that an example using N2 gas was obtained. In Examples 3 and 4, it was found that the variation in the properties of the photoconductive layer was significantly improved.

Furthermore, when the photoconductive layer formed on the Si wafer was measured for oxygen in the film using infrared absorption spectroscopy, it was found that the content of oxygen atoms was increased compared to when N2 gas was not used. Nitrogen atoms are contained in the film, but even if the amount of nitrogen atoms contained in the film is increased by increasing the flow rate of N gas, there is little effect on the optical, electrical, and photoconductive properties. It turned out that it didn't. Furthermore, no carbon content could be detected in the infrared absorption spectrum.

Example 5 B and H were further produced using the same manufacturing method as in Example 3.

/H, 10oρpa+ from the cylinder, valve 38, outlet pressure gauge 39, inflow valve 27. B, H through mass flow controller 21 and outflow valve 15.

Gas 13. H,/S i H, was introduced at a ratio of 9116 to form a photoconductive member.

The electrical, optical, and photoconductive properties of the photoconductive member obtained by the above manufacturing method were measured by the following method.

AQ on the top surface of the photoconductive layer of the photoconductive member using the substrates 6 and 7.
Form an electrode to increase dark conductivity and AMl 10 W/c+
The photoconductivity of # when light was incident was measured.

As a result, the dark conductivity of both the photoconductive members using substrates 6 and 7 was 8 4.
A very good photoconductive layer with a photoconductivity ratio of 5.4 x 104 was obtained.The optical bandgap was 2.01 aV.Substrate 8 When the charging characteristics, dark decay, and photosensitivity of the photoconductive member using the photoconductive member were measured using a paper analyzer, sufficiently good characteristics were obtained to be applicable as an electrophotographic image forming member.

[Effects] As is clear from the description of the examples above, the photoconductive member of the present invention has extremely excellent electrical, optical, and photoconductive properties. When applied as a forming member, it has a long charge retention function during charging processing, has no influence of residual potential on image formation, is stable even in a humid atmosphere, and has high photosensitivity and high SN. It has a high ratio, is resistant to light deterioration, is resistant to repeated use, has high density, excellent gradation, and can always stably obtain high-quality visible images with high resolution.

Also.

It also becomes possible to mass-produce photoconductive members without using complicated equipment or methods.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a photoconductive member according to the present invention, and FIG.
3 and 3 are diagrams showing the optical bandgap and electrical characteristics of the photoconductive member of the present invention, FIGS. 4 and 5 are diagrams showing the optical bandgap and electrical characteristics of the conventional photoconductive member, 6, 7, and 8 are diagrams showing the optical bandgap distribution of the photoconductive layer when the present invention is applied to an electrophotographic image forming member, and FIG. 9 is a diagram showing the optical bandgap distribution of the photoconductive layer of the present invention. It is a figure showing an example of the device which manufactures a member. ■...Photoconductive member 2...Support 3...Amorphous layer (photoconductive layer) Patent applicant Ricoh Co., Ltd. and one other person CO2/5iH4 CO2/5iH4 02/SiH4

Claims (1)

[Claims] 1. In a photoconductive member in which an amorphous layer having silicon atoms as a base material is provided on a support, the amorphous layer contains oxygen atoms or oxygen atoms and nitrogen atoms, and 10^-^1 ^1
It has a dark conductivity in the range of ~10^-^1^5 (Ωcm)^-^1, and is 10^-^6 to 10^-^9 (Ωcm) when light is incident at AM1 100mW/cm^2. ^-^2
has a photoconductivity in the range of A photoconductive member characterized in that it has photoconductive properties.