JPS6028659A - Photosensitive body - Google Patents

Abstract

PURPOSE:To stabilize electric characteristics on the surface of a photosensitive body, to prevent leakage of surface charge in the surfacial direction, and to prevent flow and reverse of picture image by incorporating metal atom or metal ion to a layer constituting a photosensitive body of amorphous silicon. CONSTITUTION:Metal atom or metal ion is incorporated into a layer constituting amorphous silicon photosensitive body. Suitable metal atoms are, for example, transition metals belonging to group 3b, 4b, 5b, 6b, 7b, 8, 1b, and 2b; Fe, Al, and Ni are preferred. Also, metals constituting Friedel-Craft' catalyst, such as those constituting AlCl3, SbCl5, FeCl2, FeCl3, SnCl4, TiCl4, TeCl4, BiCl3, ZnCl2, BF3, etc. are suitable.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Industrial Application Field The present invention relates to a photoreceptor, such as an electrophotographic photoreceptor.

2. Prior art Conventionally, as an electrophotographic photoreceptor, Se, or Se and As,
Photoreceptor doped with Te, Sb, etc., znO or CdS
Photoreceptors, etc., in which the compound is dispersed in a resin binder are known. However, these photoreceptors have problems in terms of environmental pollution, thermal stability, and mechanical strength. On the other hand, electrophotographic photoreceptors using amorphous silicon (a-3i) as the entire base material have been proposed in recent years. a-8i is
It has a so-called dangling bond in which the 5t-3t bond is broken, and many localized orders exist within the energy gap due to this defect. For this reason, hopping conduction of thermally excited carriers occurs, resulting in a small dark resistance, and photoexcited carriers are trapped in localized positions, resulting in poor photoconductivity. Therefore, the dangling bonds are filled by compensating the above defects with hydrogen atoms (H) and bonding H to Si.
It is called i:H. ) has extremely excellent properties as a photosensitive layer of a photoreceptor because its resistivity decreases greatly when irradiated with light in the visible and infrared regions. a-8t with base material
An electrophotographic reproduction machine incorporating a system photoreceptor is shown. According to this copying machine, the upper part of the cabinet 1 has a document 2
A glass document mounting table 3 on which the document is placed, and a platen cover 4 that covers the document 2 are provided. Below the document table 3, an optical scanning table consisting of a first mirror unit 7 equipped with a light source 5 and a first reflection mirror 6 is provided so as to be movable linearly in the horizontal direction of the drawing. The second mirror unit 20, which is used to maintain a constant optical path length, moves according to the speed of the first mirror unit, and the reflected light from the document table 3 passes through the lens 21 and the reflection mirror 8 to the image carrier. The light is incident on the photosensitive drum 9 in the form of a slit. Around the drum 9, there is a corona charger 10. Developing device 11, transfer section 12, separation section 13, cleaning section 1
The copying machine 18 is fed from the paper feed box 15 through the paper feed rollers 16 and 17, and after the toner image is transferred from the drum 9, it is further fixed in the fixing section 19, and then the toner image is fixed on the tray 3.
The paper is ejected to 5.

In the fixing section 19, the developed copy paper is passed between a heating roller 23 having a built-in heater 22 and a pressure roller 24 to perform a fixing operation.

However, as a result of the inventor's study of the a-8t photoreceptor, the following facts were discovered.

In other words, a photoreceptor having an a-8i material on its surface is exposed to the atmosphere and moisture for a long period of time, so it is susceptible to the effects of the atmosphere and moisture. Due to the influence of chemical species generated at the locations indicated by 10.12.13 in the figure, the chemical stability of the surface is poor and the following defects occur.

(1) The a-Si layer has a skeleton of 5t-8t bonds, and the bonding state is relatively good inside the layer, but on the surface side there are defects (i.e., bonds) caused by polyvalent elements (Si). There are many discontinuities or dangling bonds), and a defect ranking exists. Moreover, since a-8i is structurally hard, the above-mentioned defects once generated during film formation are retained as they are. For this reason, when used in a device as shown in Figure 1, ions, molecules, and atoms in the discharge atmosphere due to corona discharge or other atmospheres are easily adsorbed onto the surface of the a-8i photoreceptor. Electrical resistance in the surface direction decreases, making it easier for charges to leak in the surface (creeping) direction.

(2) As a result, in addition to unstable electrical and photoconductive properties, phenomena such as image deletion and white spots (white spots) occur.

That is, FIG. 2(A) shows the surface potential after exposure at the initial stage of copying, but after multiple copies, the initial potential shown by the broken line K in FIG. 2(B) changes as shown by the solid line. The potential of the exposed portion becomes gentle at the boundary with the exposed portion, and the potential itself is attenuated. This is considered to be due to the charge leak mentioned in (i) above.

(3) Further, after manufacturing the a-8i photoreceptor, hydrogen is desorbed by heat or light, which also causes the above-mentioned defects.

(4) Furthermore, the a-8i photoreceptor has poor long-term storage stability due to the above-mentioned reasons, and this must also be overcome in practical terms.

As a result of further investigation, the inventor of the present invention has concluded that the above-mentioned defect is due to the following causes.

Before the above-mentioned corona discharge, no ions, molecules or atoms are adsorbed on the surface of the photoreceptor, so the energy band of the photoreceptor is as shown in FIG.

However, when various ions activated (or stable) by corona discharge or ions in the atmosphere are adsorbed on the surface of the photoreceptor, impurity levels are formed near the surface of the photoreceptor due to this gas adsorption. As a result, the heptagonal lumi level (EF) near the surface shifts. However, since the Fermi level near the surface coincides with the 7-Elumi level inside the photoreceptor, a bend (band bending) appears in the energy band in the surface region, as shown in Figure 4. Accumulation of carriers occurs and a space charge layer is formed. Band bending occurs from the surface of the photoreceptor to the inside of the photoreceptor (particularly to a depth d of about 1 μm). Therefore, it is thought that the electrical conductivity in the creeping direction of the photoreceptor increases significantly due to the carrier accumulation phenomenon based on band bending due to gas adsorption, causing the above-mentioned image deletion. (Eo is the donor level generated by gas adsorption, EC is the conduction band, and Ev is the valence band) 〇On the other hand, a
- It is known that an electron-accepting or donating substance is adsorbed onto the surface of a Si-based photoreceptor in order to stabilize the surface and control the electrical properties. Since the acceptor or donor substance is merely adsorbed on the surface, it is easily detached from the same surface, especially during repeated use, and there is a drawback that the life of the photoreceptor cannot be extended. Furthermore, this problem may be further exacerbated because the adsorbent is composed of an organic compound and has properties significantly different from inorganic a-8t.

3. Purpose of the Invention The purpose of the present invention is to stabilize the electrical characteristics of the surface of the a-8i photoreceptor and prevent leakage of surface charge in the creeping (surface) direction, taking into account the above-mentioned special characteristics of the A-8i photoreceptor. The purpose is to satisfy various requirements such as prevention of image deletion and white spots, improvement of resolution, IvPA properties and image density, prevention of change in image quality due to repeated use, and long-term storage stability of photoreceptors.

4. Structure of the invention and its effects, that is, the present invention provides a photoreceptor characterized in that a metal atom and/or metal ion is contained in the photoreceptor constituent layer of an amorphous silicon type (a-8i thread). This is related to.

According to the present invention, since metal atoms and/or ions are contained in the a-8t layer, impurity levels or trap levels are formed near the layer surface at a very high concentration. This is considered to be a trap, and for this reason, the ions, atoms, and molecules adsorbed on the surface of the photoreceptor are trapped and fixed by the metal atoms or metal ions. In this case, the above-mentioned band bending occurs near the surface due to the formation of impurity levels by the metal atoms or ions thereof, but as shown in FIG. Shallow depth d'(((1
(i.e., the bending does not extend deep into the interior over the depth d mentioned in FIG. 4, as shown by the dashed line in FIG. 6).

Therefore, since band bending occurs only to a very shallow position, the accumulation of carriers and the formation of a space charge layer are weakened as a whole, which reduces the change in electrical conductivity in the direction along the surface of the photoreceptor, resulting in image distortion. etc. can be effectively prevented.

In order to obtain such remarkable effects, it is especially important to use metals that have incomplete d-electron shells (lack of d-orbital electrons) as the metals to be included in the a-8i layer. This is desirable in that the Tontsubu effect is good. Such metals include Group 3b, Group 4b, Group 5b of the periodic table,
Mention may be made of transition metals belonging to Group 6b, Group 7b, Group 8, Group 1b or Group 2b, such as Fe −, AZ%
Nxs, especially Fe, is desirable. However, the periodic table referred to here is from @HandbookofChemistry an
d Physics+s”, 58th (1977-1
978). In addition, as metal atoms, metals constituting Friedel-Craft catalysts are preferable, such as htct, , 5bct, , FeC62, Fe
CZs, 5nC44, TiCl2, TeCl4, Bi
Constituent metals of Friedel-Craft catalysts such as Cl2, ZnCl2, BP, etc. are mentioned.

5. Examples Hereinafter, the present invention will be described in detail with reference to examples.

7 to 8 illustrate an a-3i electrophotographic photoreceptor according to the present invention.

The photoreceptor 39 in FIG. 7 has a P-type charge blocking layer 42 made of a-3i :H heavily doped with an element of Group 3a of the periodic table, such as boron, on a conductive support substrate 41 such as At, and It has a structure in which an i-type photoconductive layer 43 made of a-8t:H light-doped with a Group 38 element, for example, boron, is laminated. The photoconductive layer 43 has a ratio of resistivity ρD in the dark to resistivity ρL during light irradiation that is sufficiently large as an electrophotographic photoreceptor, and has good photosensitivity (particularly to light in the visible and infrared regions). In addition, a Group 3a element of the periodic table, such as boron, can be mixed with a flow rate ratio (JH6/SiH4) =
Doping at 1-500 ppm makes it intrinsic, that is, L-type (resistivity is 10-10 Ω-cm).
Yes, high resistance can be achieved.

In this photoreceptor 39, according to the present invention, the outermost surface layer (or the layer near the inner side) 43a of the photoconductive layer 43 is made of the above-mentioned metal, particularly Fe atoms and/or Fe atoms.
It is extremely important that ions are contained in a predetermined amount. As mentioned above, the inclusion of such metal atoms or ions reduces the influence of adsorbed substances on the surface of the photoreceptor, reduces changes in electrical conductivity in the creeping direction, and provides stable characteristics without image blurring. You can get it.

For this purpose, it is desirable that the content of metal in the scrap 43a is 1 to 10,000 ppm based on silicon atoms. If it is less than 1 ppm, the effect will be extremely poor, and
It is thought that if it exceeds 10,000 ppm, the above-mentioned band bending region increases and the photosensitive characteristics are likely to be adversely affected. The metal content is within the above range.
5 to 500 ppm is more desirable.

Further, the thickness of the metal-containing layer 43a is preferably 50 μm to 2 μm, which is suitable for 50 to 5000 A, and 400 to 2 μm.
2000 A is more desirable.

Note that by increasing the resistance of the photoconductive layer 43 as described above, the charge retention ability can be improved. As a result, a photoconductive layer having good photosensitivity and potential holding ability can be obtained. Further, in order to sufficiently prevent the injection of electrons from the substrate 41, the charge blocking layer 42 must be
Group 8 elements (e.g. boron) at flow rate ratio JH6/5iI (=
It is preferable to dope with 500 to 000 ppm to make it P type (or even P type).

There is also an appropriate range for the thickness of each layer of the photoreceptor described above, and the photoconductive layer 42 has a thickness of 2 to 80 μm (preferably 5 to 30 μm).
μrn), the blocking layer 42 should be between 100 and 1 μm (preferably between 400 and 5ooo!). If the photoconductive layer 43 is less than 2 .mu.m, the charging potential will not be sufficient, and if it exceeds 80 .mu.m, it will be unsuitable for practical use and will result in long film formation. If the blocking layer 42 has no grooves of 100X, there will be no blocking effect, and if it exceeds 1 μm, the charge transport ability will be poor. Note that each of the above layers needs to contain hydrogen. In particular, the hydrogen content in the photoconductive layer 43 is essential to compensate for dangling bonds and improve photoconductivity and charge retention, and is usually 1 to 40 atomic %, and 10 to 40 atomic %. 3
More preferably, it is 0 atomic%. In addition, as an impurity for controlling the conductivity type of the blocking layer 42, traps other than boron are used in order to make the blocking layer 42 P-type. Ga, I
Group 38 elements of the periodic table, such as n and Tt, can be used. This blocking layer can also be N-type, for which purpose it can be doped with an element of group 5a of the periodic table, such as P 1As % 5bsBi.

The photoreceptor in FIG.
The 0a-3iC:H layer 44, which is composed of a C:H layer 44 and an a-8i:H (photoconductive) layer 43 laminated in sequence, is mainly used to maintain potential, transport charge, and improve adhesion to the substrate 41. It is preferable to have a thickness of 2 μm to 80 μm (more preferably 5 μm to 30 μm). The photoconductive layer 43 generates charge carriers in response to light irradiation, and its thickness is 3000 mm.
It is desirable that it is X~5μrn (especially 5000X~3μm1). However, it is preferable that this photoconductive layer is not doped with any impurities such as the above-mentioned boron, since the movement of carriers becomes smoother.

In the photoreceptor shown in FIG. 8 as well, a metal-containing layer 43a similar to that described above is formed on the surface area of the photoconductive layer 43, so that similar effects can be obtained.

In the photoreceptors illustrated in FIGS. 7 and 8, the metal contained in the layer 43a is particularly preferably a transition metal having an incomplete d-electron shell, and preferably Fe.

Besides, At+Ni etc. can also be used.

Further, in the above example, the metal-containing layer 43a is formed on the outermost surface area of the photoreceptor, but instead, it may be formed near the inner side of the outermost surface area. The thickness may vary.

Next, a method for manufacturing the above-mentioned photoreceptor (for example, drum-shaped) and its apparatus (glow discharge device) will be explained with reference to FIGS. 9 and 10.

Inside the vacuum chamber 52 of this device 51, a drum-shaped substrate 41
is set so as to be vertically rotatable, and a heater 55 is used to heat the substrate,
11 can be heated from the inside to a predetermined temperature. A cylindrical high-frequency electrode 57 with a gas outlet 53 is disposed around and facing the substrate 4J, and a high-frequency power source 56 generates a υ glow discharge between the electrode 57 and the substrate 41. In addition, 62 in the figure is a supply source of SiH or a gaseous silicon compound, 63 is a supply source of Fe compound gas, 64 is a supply source of hydrocarbon gas such as CH, 65 is a carrier gas supply source such as Ar, 66 is an impurity gas (e.g. B2H6 or PH
, ) supply source, 67 is each flow meter. In this glow discharge device, first, the surface of a support, for example, an At substrate 410 is cleaned, and then placed in a vacuum chamber 52.
The gas pressure inside the chamber is adjusted to 10-6' Torr, and the substrate 41 is heated to a predetermined temperature, particularly 100 to 35
Heat and maintain at 0°C (preferably 150-300°C).

Next, using a high purity inert gas as a carrier gas,
In4 or a gaseous silicon compound, a mixed gas prepared by diluting an appropriate amount of Fe compound gas, and CH4, B, H, etc. are introduced into the vacuum chamber 52, for example, from 0.01 to 10T.
The high frequency power supply 56 generates a high frequency voltage p (
For example, 13.56 MHz) is applied. As a result, each of the above reaction gases is decomposed by glow discharge between the electrode 57 and the substrate 41, resulting in a-8i:H (or a-8iC:H) and a-8iC:H.
-8i:H

In the above manufacturing method, Fe compound gas is supplied from the supply source 63 to form the Fe-containing layer 43a, and this supply mechanism is constructed as shown in FIG. 10, for example. A cylinder 63 as a supply source contains liquid pentacarbonyl iron (Fe(Co)s) indicated by D 68,
Ar gas 69 is blown into this at a controlled flow rate to cause bubbling, and this allows Fe(
Coal gas 68' is introduced into the above-mentioned glow discharge device via a flow meter 67. In this case, Fe(C) in the cylinder 63
o) The vapor pressure of s may be, for example, 34 Torrs and the temperature may be 5°C. 60 in the figure is each flow rate adjustment valve. F above
e(Co) gas is decomposed by discharge together with other reactive gases in a glow discharge device, resulting in Fe atoms or F
E ions are incorporated into the a-8i:H deposited on the substrate 41, forming the Fe-containing layer 43a described above. Therefore,
The Fe content of 438 is determined by introducing Fe(Co) as described above in the final stage after depositing a-8i:H to a predetermined thickness under conditions without introducing Fe(CO)5. Can be formed easily and accurately.

In the above manufacturing method, the support temperature is set at 100 to 350°C in the step of forming the A-8T layer on the support, so it is possible to improve the film quality (in terms of electrical characteristics) of the photoreceptor. can.

In addition, in order to compensate for dangling bonds during the formation of the a-8i-based film, Fuch is introduced in the form of SiF4 or the like in place of the above-mentioned H or in combination with H.
-8i:F, a-8t:H:F, a-8iC:F,
It can also be a-3iC:H:F. 7 in this case
The amount of twisting is 0.01 to 20 atomic chigayo (,0,
5 to 10 atomic is highly desirable.

The above manufacturing method is based on the glow discharge decomposition method, but there are also methods such as sputtering method, duon blating method, and method of evaporating Si while introducing activated or ionized hydrogen in a hydrogen discharge tube. (In particular, Japanese Patent Application Laid-Open No. 56-78413 (Patent Application No. 54-152) filed by the present applicant)
The above-mentioned photoreceptor can also be manufactured by the method of No. 455).

FIG. 11 shows a photoreceptor according to the present invention described above in JP-A-56-7.
8413. This figure shows a shrinking apparatus used for fabrication by the vapor deposition method of No. 8413.

A vacuum pump (not shown) is connected to the Pel jar 71 via an exhaust pipe 73 having a butterfly valve 72, thereby increasing the inside of the Pel jar 71 to, for example, 10 to 10 Torr.
A high vacuum state of r is established. The substrate 41 is placed inside the Pel jar 71 and heated to a temperature of 100 to 100 by the heater 75.
While heating to 350 DEG C., preferably 150 to 300 DEG C., a negative DC voltage of 0 to -10 KV, preferably -1 to -6 KV is applied to the substrate 1 by the DC power supply 76. In addition, while introducing active hydrogen and hydrogen ions into the Pel jar 71 through a hydrogen gas discharge tube 77 connected to the Pel jar 71 so that its outlet faces the substrate 41, a silicon evaporation source provided so as to face the substrate 41 is introduced. 78 and, if necessary, the aluminum evaporation source 79 and open the upper shutters S to simultaneously evaporate silicon and aluminum at an evaporation rate such that their evaporation rate ratio is, for example, 1:10-'.

Moreover, Fe (Co ) generated as described above! The gas is appropriately introduced into the discharge tube 70, where it is decomposed into Fe, and then introduced into the Pelger 71. Also, Pelger 7
CH4 gas is appropriately introduced into the layer 1 through a discharge tube (not shown), and the above-described layers 42 and 43 containing a predetermined amount of K, for example, aluminum, and the Fe-containing layer 43a are formed.

For example, the structure of the discharge tube 77, 70 is shown in FIG. 12, as shown in FIG. , a discharge space member 84 made of, for example, cylindrical glass surrounding the discharge space 83, and another ring-shaped electrode member 8 provided at the other end of the discharge space member 84 and having an outlet 85.
6, by applying a DC or AC voltage between the one electrode part 4182 and the other electrode member 86, for example, hydrogen gas supplied via the gas port 81 is discharged. A glow discharge is produced in the space 83, whereby active hydrogen and ionized hydrogen ions constituted by hydrogen atoms or molecules activated by simulonic energy are discharged through the outlet 85. Discharge space member 84 in this illustrated example
has a double pipe structure through which cooling water can flow, and 87.88 indicates the cooling water inlet and outlet. 89 is a cooling fin for one electrode member 82. The distance between the electrodes in the hydrogen gas discharge tube 77 is 10 to 15 mm, the applied voltage is 600 V1, and the pressure of the discharge amount 83 is 10 mm.
It is said to be about Torr.

Note that as another method for forming the metal-containing layer 43a described above, ion implantation (implantation) technology can be employed. That is, for example, in FIG. 7, after forming the a-8i:H photoconductive layer 43, it is placed in an ion implantation device and the surface of the photoconductive layer 43 is irradiated with ions of a predetermined metal (e.g., Co, Fe). , to form a metal-containing layer 43a in the same surface area. This metal-containing layer 43
The depth of a and the metal concentration can be arbitrarily adjusted by the implantation energy of metal ions, and by increasing the energy, a metal-containing layer can be selectively formed in the inner region near the surface of the photoconductive layer 430. As for the implantation conditions, for example, the implantation energy may be 30 KeV and the dose amount may be 1100 pp with respect to St atoms. Another advantage of this ion implantation method is that metal can be doped at room temperature without heating the substrate, and therefore metal-containing layers can be formed while eliminating adverse effects of temperature on each layer of the a-8t system.

Next, the present invention will be described with reference to specific examples.

Example 1 An electrophotographic photoreceptor having the structure shown in FIG. 7 was prepared using a drum-shaped Al support by a glow discharge decomposition method. That is, first, after cleaning the surface of the support, for example, a drum-shaped At substrate 41 having a smooth surface, it is placed in a vacuum chamber 52 shown in FIG. The substrate 41 is heated and maintained at a predetermined temperature, particularly 100 to 350°C (preferably 150 to 300°C). Next, high-purity Ar gas was introduced as a carrier gas, and high-frequency power with a frequency of 13.56 MHz was applied under a back pressure of 0.5 Torr to perform a preliminary discharge for 10 minutes. Next, a reaction gas consisting of SiH4, B, and H is introduced, and the flow rate ratio i:i:(
(Ar+SiH,+B,If6) of 1,5X10
By glow discharge decomposition of the mixed gas, the P-type a-8t:H layer 42, which plays a directional blocking function, is
A film was formed to a thickness of 1 μm at a deposition rate of hr. Subsequently, the flow rate ratio of B and H6 to SiH4 was set to 1:(IXIO
) was subjected to discharge decomposition to form a 15-μm-thick B-light Dobutlow 8i:H layer 43. After that, pentacarbonyl iron Fe(Co) having a vapor pressure of 34 Torr at 25° C. was decomposed using Ar gas. The liquid was bubbled, Fe(Co)s was introduced into the reaction tank using Ar gas as a carrier, and the flow rate ratio was 1:1:(IXIO) (Ar + SiH4 + B2
H,) is decomposed by glow discharge with mixed gas to a thickness of 100O
A Fe-containing layer 43a of X was further provided to complete the electrophotographic photoreceptor.

Using this photoconductor, images were produced on a copying machine (a modified U-Bix 3000 machine manufactured by Konishiroku Photo Industry Co., Ltd.), and the results showed good resolution, gradation, and high image density. A clear image with no blemishes was obtained. Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

Comparative Example 1 In the layer structure in Example 1, the effect of the Fe-containing layer (
That is, in order to clarify the formation of high-quality images by maintaining stable potential characteristics and surface chemical stability, a photoreceptor without an Fe-containing layer was prepared and image evaluation was performed.

As a result, image blurring occurred, there were many white spots on the image, and only images with poor resolution were obtained.

Example 2 A P-type a-8t:H charge blocking layer with a thickness of 1 μm and a B light doped a-8t:H layer with a thickness of 15 μm were formed on a drum-shaped At support by the same manufacturing method as in Example 1. In addition, a photoreceptor was prepared in which a 100OX thick a-3i:H layer containing a metal or non-metal additive was laminated thereon. F as gold A1 or non-metallic additive
A photoreceptor was prepared that was adjusted to contain eXCo, Ni, Zn, At, F, and CL in an amount of 50 to 1θOppm relative to St (according to ESCA analysis). The above additives are obtained by reacting each of the following compounds (1) to (7) with Ar as a carrier gas, and (
Ar+SiH4+B, H6) was decomposed by glow discharge together with a mixed gas and contained in the a-3i:H layer.

(1) Pentacarbonyl iron: Fe(Co)s (7I
Form I) (2) Dicarbonylcyclopentagenyl cobalt: C5Ha Co (Co)z (liquid) (3) Nitrosylcyclopentagenyl nickel 20, H, Ni
No (Liquid) (4) Dimethylzinc: Zn (CHs)z (Liquid) (5) Trimethylaluminum: At(CHs)
(Liquid) (6) Fluorine: F, (Gas) (7) Chlorine: Ct, (Gas) Using each drum made in this way, a copying machine (U
-Bix 3000 modified machine: Konishiroku Photo Industry Co., Ltd.)
The results of comparing the image quality after 100,000 consecutive copies and the light attenuation characteristics of the photoconductor (half-decrease exposure amount E)
V2) is shown in the table below. From this result, it is clear that when a predetermined amount of metal is contained according to the present invention, both image quality and sensitivity are improved.

In the above table, ◎: Good resolution and gradation of both images, high image density, and clarity.

○: Image blurring and white spots occur only in a small portion of the image.

△: Image blurring and white spots partially occur on the image.

×: Image blurring and white spots occur in areas of 50 inches or more.

Regarding Fe content, which showed the best characteristics in Example 2,
In addition to Fe (Co), 7 erocene (Fe (C5H5
)t) and iron hexafluoroacetylacetonate (F
A photoreceptor having the same layer structure as in Example 1 was prepared using e(HFA ) s ) as the Fe supply source. 7 Erocene and hexafluoroacetylacetone iron are in a solid state at room temperature, and after pulverizing them into micron-order fine particles in an Ar gas atmosphere, they are introduced into a reaction tank together with an Ar carrier gas and mixed (Ar + SiH4 + B2■e). Fe was incorporated into the a-3t:H layer by glow discharge decomposition with gas. When images were produced using these photoreceptors, clear images were obtained with no image smearing or white spots on either image, as in the case of Fe(Co). Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

Example 4 No. 8 was deposited on a drum-shaped At support by glow discharge decomposition method.
An electrophotographic photoreceptor having the structure shown in the figure was manufactured.

First, a support, for example, a drum-shaped A with a smooth surface,
After cleaning the surface of the t-substrate 410, the vacuum chamber 52 in FIG.
The gas pressure in the vacuum chamber 52 is adjusted to 10 Torr and evacuated, and the substrate 41 is kept at a predetermined temperature.
Especially from 100 to 350°C (preferably from 150 to 300°C)
) and keep it heated. Next, high-purity Ar gas was introduced as a carrier gas, and a high frequency power of 13.56 M (frequency 13.56 M) (z) was applied under a back pressure of 0.5 Torr.
A preliminary discharge was performed for 1 minute.

Next, a reactive gas consisting of SiH4 and CH4 is introduced, and the a-8iC:H layer which plays a charge transport function is decomposed by glow discharge at a flow rate ratio of 1:1:1 (Ar+SiH4+CH4). Thickness 1 at deposition rate
A film was formed to a thickness of 5 μm.

Subsequently, the supply of CH4 was stopped and only SiH4 was decomposed by discharge to form a non-doped a-St:H charge generation layer with a thickness of 1 μm, and then heated to 34 Torr at 25°C with Ar gas.
Pentacarbonyl iron Fe(Co)s with vapor pressure of r
Fe(C) liquid is bubbled and Ar gas is used as carrier.
o) s was introduced into a reaction tank and decomposed by glow discharge together with SiH4, and an Fe-containing layer with a thickness of 100OX was further provided to complete an electrophotographic photoreceptor.

Using this photoreceptor, we produced an image using a copying machine (U-Bix3000i manufactured by Konishiroku Photo Industry Co., Ltd.). As a result, there was no image blurring, no white spots on the image, and good resolution and gradation. Clear images with good image density and no capri were obtained. Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

Comparative Example 2 A photoreceptor with a functionally separated layer structure in Example 4, in which Fe
In order to clarify the effect of the Fe-containing layer (ie, high-quality image formation by maintaining stable potential characteristics and surface chemical stability), a photoreceptor without the Fe-containing layer was prepared and image evaluation was performed. As a result, image blurring occurred, there were many white spots on the image, and only images with poor resolution were obtained.

[Brief explanation of drawings]

1 to 5 show conventional examples, and FIG. 1 is a schematic sectional view of a conventional electrophotographic copying machine, and FIGS.
B) is a graph showing the change in surface potential of the a-8ii photoreceptor after exposure. FIG. 3 is an energy band diagram of the photoreceptor before gas adsorption, FIG. 4 is an energy band diagram after gas adsorption, and FIG. 5 is a diagram showing the electronic state density. 6 to 12 show examples of the present invention, in which FIG. 6 is an energy band diagram of a photoreceptor, FIGS. 7 and 8 are cross-sectional views of each a-8l system photoreceptor, FIG. 9 is a schematic sectional view of a glow discharge device, FIG. 10 is a schematic sectional view of an Fe compound gas supply source, FIG. 11 is a schematic sectional view of a vacuum evaporation device, and FIG. 12 is a sectional view of a gas discharge tube. . In addition, in the reference numerals shown in the drawings, 39......a-8i system bad sensitivity 41...
......Support (substrate) 42...
- Blocking layer 43...Photoconductive layer 43a...Metal-containing layer 44...Charge transport layer 55... ..... Heater 56 ..... High frequency power supply 57 ..... Electrodes 62 to 66 ..... Each gas supply source 70, 77 .... ...Gas discharge tube 78.79...It is an evaporation source. Agent Patent Attorney Hiroshi Aisaka (and 1 other person) Figure 1 Figure 2 Figure 4 R Figure 5 Figure 6 Figure 8, 39 Figure 10

Claims (1)

[Scope of Claims] 1. A photoconductor characterized in that an amorphous silicon-based photoconductor constituent layer contains metal atoms and/or metal ions. 2. Claims in which the metal atom is a transition metal belonging to Group 3b, Group 4b, Group 5b, Group 6b, Group 7b, Group 1b or Group 2b of the Periodic Table. The photoreceptor described in item 1. 3. The photoreceptor according to claim 1, wherein the gold FiN particles are a metal constituting the Riederkraut catalyst. 4. The content of metal atoms and/or metal ions is 1 to 10. The photoreceptor according to any one of claims 1 to 3, which is OOOPflm. 5. The amorphous silicon-based photoreceptor according to any one of claims 1 to 4, wherein the outermost surface layer or a layer near the inner surface thereof contains metal atoms and/or metal ions. Photoreceptor. 6. The photoreceptor according to claim 5, wherein the layer containing metal atoms and/or metal ions has a thickness of 50 A to 2 μm.