JPS6028658A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve surface potential characteristics of a photosensitive body and preservability of the surface potential characteristics for a long time by incorporating metal atom or metal ion into the surface protecting layer an amorphous Si photosensitive body. CONSTITUTION:Metal atom and/or metal ion is (are) incorporated into the surface protecting layer of an amorphous Si photosensitive body. Preferred metal atoms are atom of transition metal of the group 3b, 4b, 5b, 6b, 7b, 8, 1b, 2b. Metals constituting Friedel-Crafts' catalyst such as AlCl3, SbCl5, FeCl2, FeCl3, SnCl4, TiCl4, TeCl4, BiCl3, ZnCl2, BF3, etc. are more preferable.

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, M, as a child photoreceptor, Se or 5eK
Photoreceptor doped with As-Te, Sb, etc., ZnO, Cd, etc.
Photoreceptors, etc. in which S 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-8t) as a base material have been proposed in recent years. a-8
No. 1 has a so-called dangling bond in which the 8l-8l bond is broken, and many localized levels 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 levels, resulting in poor photoconductivity. Therefore, the above defect is replaced by a hydrogen atom σD
The dangling bonds are filled by compensating with and bonding 5IKH.

Such amorphous hydrogenated silicon (hereinafter referred to as a-8
It is called t:H. ) has extremely excellent properties as a photosensitive layer of a photoreceptor because its resistivity decreases greatly when it is irradiated with light in the visible and infrared regions.

Figure 1 shows the above a-8i:H as the base material and the a-8i
An electrophotographic reproduction machine incorporating a system photoreceptor is shown.
According to this copying machine, a glass document mounting table 3 on which a document 2 is placed and a platen cover 4 that covers the document 2 are disposed in the upper part of a cabinet 1. 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 in a straight line in the left and right direction of the drawing. A second mirror unit 20 for making the optical path length constant 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 and is reflected as an image carrier. The light is incident on the photosensitive drum 9 in the form of a slit. A corona charger 1 is installed around the drum 9.
0. A developing device 11, a transfer section 12, a separation section 13, and a cleaning section 14 are arranged, and the copying machine 18, in which the paper is sent from the paper feed box 15 through the respective paper feed rollers 16 and 17, transfers the toner image on the drum 9. Afterwards, the image is further fixed in the fixing unit 19, and the paper is discharged to the tray A5. In the fixing section 19, the heater 2
A fixing operation is performed by passing the developed copy paper between a heating p-roller 23 containing a built-in roller 2 and a pressure roller 24.

However, as a result of the inventor's study of the above a-S1 type photoreceptor, the following fact was found.

That is, the photoreceptor has a surface impregnated with an a-8l type substance.

Because it is exposed to the atmosphere and humidity for a long period of time, it is susceptible to the effects of the atmosphere and humidity, and the copiers in the electrophotographic process described above.
discharge (particularly the locations indicated by 10.12.13 in Figure 1)
Due to the influence of chemical species generated in the process, the chemical stability of the surface is poor, and the following defects occur.

(The 11a-8t layer has a skeleton of bonds between 5t-81, and the bonding state is relatively good inside the layer, but on the surface side, there are defects (i.e. bond discontinuities) caused by multivalent elements (Sl). dangling bonds), and there are defect levels.Moreover, since -a-81 is structurally hard, the defects once generated during film formation are retained as they are. When used in a device as shown in FIG. 1, ions and molecules in the discharge atmosphere due to corona discharge or other atmospheres.

Atoms are easily adsorbed on the surface of the A-8L photoreceptor.

The electrical resistance in the direction of the surface decreases and charges are transferred to the surface (creepage).
It becomes easy to leak in the direction.

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

That is, although FIG. 2 (5) shows the surface potential after exposure at the initial stage of copying, after multiple copies, the initial potential shown by the broken line in FIG. The potential becomes gentle at the boundary with the exposed portion, and the potential itself attenuates. This is considered to be due to the charge leak mentioned in (1) above.

(3) Furthermore, hydrogen is desorbed from the a-S 1 photoreceptor due to heat or light after manufacturing, which also causes the above-mentioned defects.

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

As a result of further investigation, the inventors of the present invention have concluded that the above-mentioned defects are 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 copulative discharge or ions in the atmosphere are adsorbed on the surface of the photoreceptor, impurity units are formed near the surface of the photoreceptor due to this gas adsorption. , As a result, the Fermi level (E,) near the surface shifts. However, since the Fermi level near the surface matches the Fermi level inside the photoreceptor,
As shown in FIG. 4, a bend (hand bending) appears in the energy band in the surface region, and this band bending causes accumulation of carriers and forms a space charge layer. band bending.

It occurs from the surface of the photoreceptor to the inside (particularly to a depth d of about 1 μm). Therefore, it is thought that the accumulation phenomenon of carriers based on band bending due to such gas adsorption significantly increases the electric conductivity in the creeping direction of the photoreceptor, causing the above-mentioned image deletion. FIG. 5 shows the electronic state density of the photoreceptor after gas adsorption (ED is the donor level generated by gas adsorption, Be is the conduction band, and Ev is the valence band).

On the other hand, there is known an a-8i photoreceptor in which an electron-accepting or donating substance is adsorbed onto the surface to stabilize the surface and control the electrical properties.

However, since the electron-accepting or donating substance is simply adsorbed on the surface of the photoreceptor, it is likely to be detached from the surface, especially during repeated use, and the life of the photoreceptor may not be that good. There are drawbacks. Moreover, this problem may be further exacerbated because the adsorbent is composed of an organic compound and has properties significantly different from inorganic a-81.

3. Purpose of the Invention The purpose of the present invention is to stabilize the electrical characteristics of the surface and improve the creepage (
Prevention of leakage of surface charge in the surface direction 1. Prevention of image deletion and white spots, improvement of resolution, gradation and image quality, prevention of changes in image quality due to repeated use, long-term storage stability of photoreceptors, etc. The goal is to satisfy the following.

4. Structure of the invention and its effects: 1. The present invention is an a-8i photoreceptor having an amorphous silicon-based (a-8i-based) surface protection layer, wherein the surface preservation layer contains metal atoms and/or Or it relates to a photoreceptor characterized by containing metal ions.

According to the present invention, an a-8i-based surface protective layer (particularly, for example, 7-T: Rufus hydrogenated silicon carbide (a-8IC:
H) is provided with a surface modified layer consisting of a
It is possible to eliminate the drawbacks regarding the surface characteristics of the -8i photoreceptor. That is, the surface protective layer improves the surface potential characteristics of the a-8i photoreceptor, maintains the potential characteristics over a long period of time, maintains environmental resistance (prevents the influence of humidity, atmosphere, and chemical species generated by corona discharge), It has functions such as improving printing durability due to its high surface hardness, improving heat resistance when using a photoreceptor, and improving thermal transferability (especially adhesive transferability), and functions as a surface modification layer.

Furthermore, since metal atoms and/or ions are contained in this surface protective layer, impurity levels or trap levels are formed near the layer surface at a considerably high concentration. For this reason, ions, atoms, and molecules adsorbed on the surface of the photoreceptor are trapped by the metal atoms or metal ions.

It is thought that it will be fixed. In this case, the above-mentioned band bending occurs near the first surface due to the formation of impurity levels by the metal atoms or their ions, but the sixth
As shown in the figure, the metal atoms or their ions cause band bending only up to a very small distance d'(<<1 μm) from the surface of the photoreceptor (i.e., as shown by the broken line in FIG. (Benting does not extend deep into the interior over the depth dK mentioned in the figure).Therefore, band bending occurs only to a very shallow position, so carrier accumulation and space charge layer formation are weak overall. is,
This reduces changes in electrical conductivity in the longitudinal direction of the photoreceptor, thereby effectively preventing image deletion and the like.

In order to obtain such remarkable effects, the above-mentioned metals to be included in the a-8i-based surface protective layer are particularly those having an incomplete d-electron shell (lack of d-orbital electrons).
This is desirable because it provides a good trapping effect for adsorbed molecules.

Such metals include Groups 3b and 4b of the periodic table,
Groups 5b and 6b.

Transition metals belonging to groups 7b, 8, 1b or 2b may be mentioned, such as Fe, Ni, especially F
e is desirable. However, the periodic table referred to here is “Handb
ookof Chemistry and Physi
cs' 58 th (1977-1978). In addition, metals constituting a free-solat fluorocarbon catalyst are good examples of gold atoms, such as AA'C1h, 5bcl, -FeCj?
t, FeC15,5nC4-TlC1,, TeC4
, B1C11, ZnC7+2, BF3, and the like, which are constituent metals of Friedel-Craft catalysts.

5. Examples EMBODIMENT OF THE INVENTION Below, one embodiment of the present invention will be described in detail.

FIGS. 7 and 8 illustrate an electrophotographic photoreceptor of the a-81 type according to the present invention.

The photoreceptor 39 in FIG. 7 has a P-type material blocking layer 42 made of a-8i:H heavily doped with an element of group 38 of the periodic table, such as boron, on a conductive support substrate 41 such as i, and An L-type photoconductive layer 43 made of a-8L:H lightly doped with a Group 38 element, such as boron, and a surface-modified layer 45 made of amorphous hydrogenated silicon nitride (a-8IN:H) are bonded to each other. It consists of a

The photoconductive layer 4.3 has a dark resistivity ρ. The ratio of resistivity ρ at the time of light irradiation is large enough for an electronic Zg photoreceptor to achieve photosensitivity (
Particularly good against visible and infrared light. In addition, by doping an element from Group 38 of the periodic table, such as boron, at a flow rate ratio (B, 11°/5II(4) = 1 to 500), it can be made intrinsic, that is, 1 (specific resistance to 11 to 1012 Ω-F). Yes, high resistance can be achieved.

In this photoreceptor 39, a photoconductive layer 4 is formed based on the present invention.
The above-mentioned metal, especially F
It is extremely important that a predetermined amount of e atoms and/or Fe ions be contained. 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 metal content in one layer 45a is 1 to 10,000 JP per silicon atom.

If it is less than IPIIm, the effect will be extremely poor, and if it is less than 10
,000 solutions, it is thought that the above-mentioned band bending region increases and the photosensitive characteristics are likely to be adversely affected. The metal content is between 5 and 50 within the above range.
A zero solution is even more desirable. The thickness of the first surface modified layer 45 is preferably 50 to 500X, and 400 to 2000X.
is even more desirable. This surface modification layer 45 improves the surface potential characteristics of this photoreceptor, maintains the potential characteristics over a long period of time, and maintains environmental resistance (humidity and atmosphere).

It has functions such as preventing the influence of chemical species generated by corona discharge), improving printing durability due to high surface hardness, improving heat resistance when using 1M & light body, and improving thermal transferability (especially adhesive transferability). However, it functions as a surface modification layer, so to speak.

Note that the charge retention ability of the photoconductive layer 43 can be improved by increasing the resistance as described above.

As a result, a photoconductive layer having good photosensitivity and good potential holding ability can be obtained. In addition, in order to sufficiently prevent the injection of electrons from the substrate 41, the charge locking layer 42 must contain an element of group 38 of the periodic table (for example, horn) at a flow rate of Bt.
It is preferable to dope with H6/SIH=500 to 100.000 to make it P-type (or even Pl-type). There is also an appropriate range for the thickness of each layer of the photoreceptor mentioned above.
The photoconductive layer 4z has a thickness of 2 to 80 μm (preferably 5 to 30 μm)
)-Ppnocking layer 42 should be 1oo'j, -xttm<desired<c4oo-5000X>t-c.

When the photoconductive layer 43 is less than 2 μm, the band 'W! The L potential is not sufficient, and exceeding 80 μm is not practical, and it takes time to form a film.

If the thickness of the dipping layer 42 is less than 100×, there will be no dipping 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.
It is 40 atomle%.

More preferably, it is 10 to 30 atomic%.

Also, the conductor 1 of the throbbing layer 42! In addition to horn, Al is used as an impurity to control the L-type to make it P-type.
.

Group 3a elements of the periodic table, such as Ga, In, and TI, can be used.

This p7 king layer can also be N-type, and for this purpose it can be doped with elements of group 58 of the periodic table, such as P, As, Sb%B1.

The photoreceptor in FIG. 8 has a first A-
8IC: H layer 44, a-81: H (photoconductive) layer 43, and second a-S'iC: 8 layer 46 are laminated in this order. First a-8 IC: H layer 44
has the functions of mainly maintaining electric potential, transporting aliphatic substances, and improving adhesion to the substrate 41, and is preferably formed 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 3oooX.
~5 μm (particularly 5000×~3 μm) is desirable. However, it is preferable that this light guide layer is not doped with impurities such as the above-mentioned horn at all, since carrier movement becomes smoother.

In the photoreceptor shown in FIG. 8, the second a-8iC:8 layer 46 has the same surface modification effect as the above-mentioned a-8IN:H layer 45, but at least a part of the area 46
A contains a metal in the same manner as described above, and thereby the same effects as described above can be obtained.

In the photoreceptor illustrated in FIGS. 7 and 8, the metal contained in the first layer 45& and 46a is particularly preferably a transition metal having an incomplete di-shell, and Fe is preferable. other,
Al, N1, etc. can also be used.

Further, the depth of the metal-containing layers 45a and 46a is preferably 50X or more, but may extend to the entire thickness of the surface protection layers 45 and 46.

In addition, in the example of FIG. 7, the surface modified layer 45 is a-8IC.
:H, the surface modified layer 46 is a-8I in the example of FIG.
They may be formed using N:H, respectively. The constituent materials of the surface modified layer are not limited to those mentioned above, and examples include a-sto:Hla SIO:
H:F, a-8IO:F may be used.

In addition, in FIG. 8, the charge transport layer 44 may be lightly doped! It is also possible to form a jumping layer (for example, an a-8iC:H layer heavily doped with horn) as shown in FIG. 7 between the cargo transport layer 44 and the substrate 41.

Next, a method for manufacturing the above-mentioned photoreceptor (eg, drum-shaped) and its apparatus (glue 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 the substrate 4 is heated by a heater 55.
1 can be heated to a predetermined temperature from the inside.

A cylindrical high frequency electrode 57 with a gas outlet 53 is disposed around and facing the substrate 41, and a glow discharge is generated between the electrode 57 and the substrate 41 by a high frequency power source 56. In addition, 62 in Figure 1 is a supply source of 5IH4 or gaseous silicon compound, 63 is a supply source of Fe compound gas, and 64 is CH4
Hydrocarbon gases such as NH, -N.

65 is a carrier gas supply source such as Ar, 66 is an impurity gas (e.g. B, Ru or PH
, ) supply source, 67 is each flow meter. In this glue discharge device, first, the surface of the support, for example, the KL substrate 41, is cleaned and then placed in the vacuum chamber 5z.
The gas pressure inside 2 is adjusted to 10 Torr and evacuated, and the substrate 41 is heated to a predetermined temperature, especially 100 to 35 Torr.
Heat and hold at 0°C (preferably 150 to 300°C).

Next, using a high purity inert gas as a carrier gas,
SiL or a gaseous silicon compound, a mixed gas prepared by diluting an appropriate amount of Fe compound gas, and CH4 (or NHs
, N! ), B2H6, etc. are appropriately introduced into the vacuum chamber 52, and a high frequency voltage (for example, 13.s 6M
Hz) is applied. As a result, each of the above reaction gases is decomposed by glue discharge between the electrode 57 and the substrate 41, and a-
8l:H (or a-8IC:H), a-8l:H, Fe
Containing a-8IN:H or a-8iC:H in the above layer 42
(or 44), 43, 45, or 46 to deposit K continuously on the substrate (ie, corresponding to the lateral pressure in FIGS. 7-8).

In the above manufacturing method, Fe-containing layer 45a or 4
In order to form 6a, Fe compound gas is supplied from a supply source 63, and this supply mechanism is constructed as shown in FIG. 1O, for example. In other words, there is 6 in the pump 63 as a supply source.
Liquid pentacarbonyl iron (Fe (Co
) s ) is contained, and Ar gas 69 is blown into it at a controlled flow rate to cause bubbling, thereby Fe(Co)g gas 68' is sent to the above-mentioned glow discharge device via the flow meter 67 using Ar as a carrier gas. Introduce. in this case,
The vapor pressure of Fe(CO)5 in the cylinder 63 is, for example, 34
Torr, and the liquid temperature may be 25°C.

60 in the figure is each flow rate adjustment valve. The above Fe'(C
o) A gas is decomposed by discharge together with other reaction gases in a glue discharge device, and the resulting Fe atoms or Fe ions are deposited on the substrate 41.
The above Fe-containing layer 45a or 46a is formed. Therefore, the Fe-containing layer 458 or 46a is Fe (Co
) a-8IN:H or a-8I under the condition that s is not introduced.
C:Fe(Co) is deposited at the final stage after depositing H to a predetermined thickness.
) can be easily and accurately formed by introducing the button as described above.

In the above manufacturing method, the support temperature is set at 100 to 350°C in the step of forming the A-8L layer on the support, so the film quality (especially electrical properties) of the photoreceptor can be improved. .

In addition, in order to compensate for the /7° ring pound when forming the above a-Si system film, it is necessary to use fluorine in the form of SIF, etc. in place of () above, or in combination with H. introduced, a-81:F, a-8t:H:F, a-
3IN:F, a-8IN:H:F= a-8iC:F,
It can also be a-8IC:H:F. In this case, the amount of fluorine is 0.01 to 20 atomic%.
, 0.5 to 10 atomlc% is more desirable.

Note that the above manufacturing method is based on the pressure glue discharge decomposition method, but other methods include sputtering method, ion blating method, and evaporating St while introducing activated or ionized hydrogen in a hydrogen discharge tube. Method (in particular, Japanese Patent Application Laid-Open No. 56-78413 (Patent Application No. 54-152) by the present applicant)
The above photoreceptor can also be produced by isobaric method (method of No. 455).

FIG. 11 shows a photoreceptor according to the present invention in the above-mentioned Japanese Patent Application Laid-Open No. 56-7.
This figure shows a vapor deposition apparatus used for fabrication by the vapor deposition method of No. 8413.

The Pel jar 71 is connected to a vacuum pump (not shown) via an exhaust pipe 73 having butterfly valves 72, thereby causing the inside of the Pel jar 71 to be pumped, for example, from 0-3 to 10.
” Set the TorrO high vacuum state. The Pelger 7 concerned
A substrate 41 is placed inside the substrate 1 and heated by a heater 75 to a temperature of 100 to 350°C, preferably 150 to 300°C.
A negative DC voltage of 0 kV, preferably -1 to -6 kV is applied. In addition, active hydrogen and hydrogen ions are introduced into the Pel jar 7e from the hydrogen gas discharge chamber 77, which is connected to the Pel jar 71 so that the outlet faces the substrate 41. The evaporation source 79 and, if necessary, the aluminum evaporation source 79 are heated and the upper shutters S are opened to simultaneously evaporate silicon and aluminum at an evaporation rate such that the evaporation rate ratio is, for example, 1:10-'.

In addition, the Fl(Co)I gas generated as described above is appropriately introduced into the discharge tube 70, where it is decomposed into Fe, and then introduced into the Pel jar 71. Also, to Pelger 71, there is a release 1! which is not shown in the figure. N2 gas is appropriately introduced through the pipe, thereby forming the above-mentioned layers 42, 43, 45 containing a predetermined amount of aluminum, and the Fe-containing layer 45a, for example.

For example, the structure of the discharge tube 77.7o described above is
Regarding 771C, as shown in Figure 12, the gas population is 81
One electrode member 82 having a cylindrical shape and this one electrode member 82 were provided at one end. A discharge space member 84 made of, for example, cylindrical glass that surrounds the discharge space 83;
4, and a ring-shaped other electrode member 86 having an outlet 85 provided at the other end of the electrode member 86, and a DC or AC voltage is applied between the one electrode member 82 and the other electrode member 86. As a result, for example, hydrogen gas supplied via the gas supply 81 causes a glow discharge in the discharge space 83,
As a result, active hydrogen consisting of hydrogen atoms or molecules activated by electron energy and ionized hydrogen ions are discharged from the outlet 85. The discharge space member 82 in this illustrated example has a double pipe structure and is configured to allow cooling water to flow therethrough, and 87 and 88 indicate a cooling water inlet and an outlet. 89 is a cooling fin for one electrode member 82.

The distance between the electrodes in the above hydrogen gas discharge tube 77 is lO
~15α, the applied voltage is 600V, and the pressure in the discharge space 83 is approximately 10'' Torr.

Note that as another method for forming the metal-containing layer 45a or 46a described above, ion implantation (implantation) technology can be employed. That is, for example, in FIG. 7, a-8
After forming the IN:H surface modification layer 45, it is placed in an ion implantation device and ions of a predetermined metal (for example, Co, Fe) are irradiated onto the surface of the surface modification layer 45 and implanted into the same surface area. , forming a metal-containing layer 45a. The depth and metal concentration of this metal-containing layer 45a can be arbitrarily adjusted by the implantation energy of metal ions, and if the energy is increased, the metal-containing layer can be selectively deposited in the inner region of the modified layer near the surface of the modified layer 450. Can be formed.

For example, the driving condition is to set the driving energy to 30
KeV, the dose is 81 atoms and 1001111
It may be set as 1. Other advantages of this ion implantation method are:

It is possible to dope a metal at room temperature without heating the substrate, and therefore to form a metal-containing layer while eliminating the adverse effects of temperature on each layer of the a-S I system.

The present invention will be explained below with reference to specific examples.

Example l The seventh layer was deposited on a drum-shaped Al support by glue discharge decomposition method.
An electrophotographic photoreceptor having the structure shown in the figure was manufactured.

That is, first, after cleaning the surface of the support, for example, a drum-shaped AJ substrate 41 having a smooth surface, it is placed in a vacuum chamber 52 shown in FIG. '
Torr and exhaust the substrate 41.
at a predetermined temperature, especially from 100 to 350°C (preferably 15°C)
Heat and maintain at a temperature of 0 to 300°C. Next, high purity A
Introducing r gas as carrier gas, 0.57"orr
A high-frequency power with a frequency of 13.56 MK was applied under a back pressure of 13.56 MK, and a preliminary discharge was performed for 10 minutes. Then 5i
A reaction gas consisting of I(4 and B!out) was introduced, and the flow rate ratio was 1.
:l: (1,5X 10-') of (Ar+5IH4+
BtHe) P-type a-81:H layer 4, which plays a charge pulling function, is created by decomposing the mixed gas by glue discharge.
2 was deposited to a thickness of 1 μm at a deposition rate of 6 pm/hr. Subsequently, a mixed gas with a flow rate ratio of B and H to SIH of 1: (I x 1O-5) was subjected to discharge decomposition to form a B-light doped a-81:H with a thickness of 15 μm.
After forming the layer 43, 34To was heated at 25°C using Ar gas.
Pentacarbonyl iron Fe(Co) with vapor pressure of rr
s liquid is bubbled and Fe(
Co)s is introduced into the reaction tank under pressure, and at the same time nitrogen gas is introduced,
At a flow rate ratio of 1:1:5 (Ar+S), the supply of B, H, and
iH4+N! ) A goo-discharge decomposition was carried out with the mixed gas, and an a-8IN:H surface protective layer 45 containing Fe was further provided to a thickness of 100X to complete an electrophotographic photoreceptor. Using this photoreceptor, images were produced using a copying machine (a modified U-Bloc 3000 machine manufactured by Konishiroku Photo Industry Co., Ltd.), and the results showed that the resolution was good in one gradation, the image density was high, and there was no capri. A clear image was obtained. Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

Comparative Example l In order to clarify the effect of containing Fe in the a-8iN:H surface retention layer in the layer structure of Example IK,
A photoreceptor was prepared in which a surface protective layer containing no . As a result, initially a clear image with good resolution and gradation was obtained, but when repeated copies were made, good quality images could only be obtained 30,000 times in a row.

Example 2 An electrophotographic photoreceptor having the structure shown in FIG. 8 was prepared on a drum-shaped AJ support by a glue discharge decomposition method. First, after cleaning the surface of a support, for example, a drum-shaped KL substrate 41 having a smooth surface, it is placed in a vacuum chamber 52.
The gas pressure inside the chamber is adjusted to 10-' Torr, and the substrate 41 is heated to a predetermined temperature, particularly 100 to 350°C.
(preferably 150 to 300"C) IC heating and maintenance.

Then, high purity Ar gas was introduced as a carrier gas and the frequency was 13.56 under a back pressure of 0.5 Torr.
A high frequency power of MH, was applied, and preliminary discharge was performed for 10 minutes.

Next, a reaction gas consisting of SIH and CH4 was introduced, and the flow rate ratio of (A r + s l H4 + C) was 1:1:1.
H4> By decomposing the mixed gas by glue discharge, the a-8IC:H layer 44, which plays a charge transport function, is separated by 911 m /
A film was formed to a thickness of 15 μm at a deposition rate of br. Subsequently, the supply of CH4 was stopped and only 5IH4 was decomposed by discharge.
Non-doped a-81 with a thickness of 1 μm: HIE charge generation layer 43
After forming 34 Torr at 25°C with Ar gas.
A liquid of pentacarbonyl iron Fe(Co)e having a vapor pressure of
o) Introduced a into the reaction tank and at the same time supplied CH4 again, co-trapping with (Ar+SiH4+CH,) mixed gas at a mixing ratio of l:l:4. -8IC:H surface protection layer 46 was further provided to complete the electrophotographic photoreceptor. Using this photoreceptor, a copying machine (U-Bix 3000 modified machine: Konishiroku Photo Industry)
As a result, a clear image with good resolution and gradation, high single image density, and no capri was obtained. Further, even after repeated copying 300,000 times, stable and high quality images were continuously obtained.

Comparative Example 3 In the photoconductor having the functionally separated layer structure in Example 2, a-
8IC:H In order to clarify the effect of containing Fe in the surface protective layer, a photoreceptor was prepared in which a surface protective layer not containing Fe was provided, and image evaluation was performed. As a result, initially, a clear image with good resolution of 5 gradations was obtained, but when repeated copying was performed, a good quality image could only be obtained 100,000 times in a row.

Example 3 Using the same manufacturing method as in Example 2, a 15 μm thick a-8iC:H charge transport layer and a nozzle size of 1 were deposited on a drum-shaped A6 support.
After forming the μm non-doped a-8L:HK charge generation layer, a 100X thick a-8IC:H surface protection layer containing metal or non-metallic additives is further formed. A photoreceptor was prepared through a process. As metal or non-metal additives, Fe=Co%Nl, Zn, AJ and F,
A photoreceptor was produced which was adjusted to contain 50 to 100 IIIXI to 5IIC (according to ES CA analysis).

The above additives include the following compounds (11 to (7)).
is introduced into the reaction tank as a carrier gas.1. Simultaneously busy again C
(Ar + S I
H4+C)I4) was decomposed by glow discharge together with a mixed gas and incorporated into the a-8IC:H surface protective layer.

(11pentacarbonyliron: Fe(CO)m (liquid) (21dicarbonylcyclopentadienyl cobal)
: CBHffiCO(Co)2 (liquid) (3) Nitrosylcyclopentagenyl Nickel: C6H5N
I No (Liquid) (4) Dimethylzinc: Zn (CH3)2 (Liquid)
(5) Trimethyl aluminum: i (CH3)
(Liquid) (6) Fluorine diF! (Gas) (7) Chlorine: CJ2 (Gas) The results of comparing the image quality after 200,000 continuous copies and the light attenuation characteristics of the photoreceptor (half-exposure iE%)
is shown below.

◎ in the above table: Both images have good resolution and gradation, and one image density is high and clear.

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

△: Image blurring and white spots partially occur.

×: Image blurring occurred on the image, and partial pressure of 50 inches or more of white spots occurred.

The above results show that when a predetermined amount of metal is contained in the surface protective layer according to the present invention, both image quality and sensitivity are improved.

Example 4 Regarding Fe content, which showed the best characteristics in Example 3,
In addition to Fe(Co)s, F2-7, (Fe(CaHI)
I)t) and iron hexafluoroacetylacetonate (F
A photoreceptor having the same layer structure as in Example 2 was prepared using (HFA)s) as the Fe supply source. , 7 Epthene and hexaflurylacetylacetone 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 (Ar + S iH<+CM< ) Fe is decomposed by glue discharge together with mixed gas to a-8iC:H
It was contained in the layer. When images were produced using these photoreceptors, clear images were obtained with no upper pressure image blurring or white spots in the same image as in the case of Fe (Code). Even after copying, stable, high-quality images were continuously 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. FIG. 2 (5), 2) is a graph showing the change in surface potential of a-3t type bad sensitivity after exposure. Figure 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 photoconductor, FIGS. 7 and 8 are cross-sectional views of each a-8i photoconductor, FIG. 9 is a schematic sectional view of the glue discharge device, and FIG. 10 is a schematic sectional view of the Fe compound gas supply source. FIG. 11 is a schematic cross-sectional view of the vacuum evaporation apparatus. FIG. 12 is a cross-sectional view of the gas group IT. In addition, in the symbols shown in one drawing, 39......a-8i type photoreceptor 41...
......Support (substrate) 42...
- Blocking layer 43...Photoconductive layer 44...Charge transport layer 45.46...Surface modification layer (surface acquisition layer) 45a
, 46a...Metal-containing layer 55...φ...Heater 56...High frequency [source 57......Electrodes 62-66 ...Each gas supply source 70, 77...Gas discharge tube 78, 79...Evaporation source. Agent Patent Attorney Hiroshi Aisaka (and 1 other person) Figure 1 Figure 2 Figure 3 "C face angle Figure 4 [r Figure 5 Figure 6 Figure 8! Figure 10 Ri゛jl-Kih' Go to W↑

Claims (1)

[Scope of Claims] 1. An amorphous silicon-based photoreceptor having an amorphous silicon-based surface protective layer, characterized in that the surface protective 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 8, Group 1b or Group 2b of the periodic table. The photoreceptor described in item 1. 3. The metal atom is a metal constituting the 7-Riedelcla 7-no catalyst. A photoreceptor according to claim 1. 4. Content of metal atoms and/or metal ions. l~I Olo 00- for silicon atoms,
A photoreceptor according to any one of claims 1 to 3. 5. The amorphous silicon-based surface protective layer is amorphous hydrogenated and/or fluorinated silicon carbide. amorphous hydrogenated and/or fluorinated silicon nitride,
Alternatively, the photoreceptor according to any one of claims 1 to 4, which is made of amorphous hydrogenated and/or fluorinated silicon oxide. 6. The photoreceptor as described in any one of claims 1 to 5, wherein the surface protective layer containing metal atoms and/or metal ions has a thickness of 50 to 500X.