JPS6098441A - Production of photosensitive body - Google Patents

Abstract

PURPOSE:To enable stabilization of the electrical characteristic on the surface of a photosensitive body by forming a layer for constituting a photosensitive body of a-Si contg. a prescribed metal for trapping an impurity and/or the ion thereof by vapor deposition or sputtering of said metal or the compd. thereof. CONSTITUTION:The impurity level or trap level of a layer 43a contg. a metal atom and/or metal ion is formed near the layer surface at a fairly high concn. by which the ion, atom and molecule adsorbed on the surface of a photosensitive body 39 are trapped by the metal atom or metal ion and are thus fixed. The accumulation of a carrier or the formation of a space charge layer is weakened overall and the change in the electrical conductivity in the creeping direction of the body 39 is decreased by which the flow of the image, etc. are eventually and effectively prevented. The transition metals belong to the IIIb, IVb, Vb, VIb, VIIb, VIIIb, I b, or IIb group of periodic table are particularly enumerated as the metal having such a remarkable effect and the metal constituting a Friedel-Crafts catalyst is preferred as the metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Industrial Application Field The present invention relates to a method for manufacturing a photoreceptor (eg, an electrophotographic photoreceptor).

2. Prior Art Conventionally, as an electrophotographic photoreceptor, Se- or As-
Photoreceptors doped with Te-8h or the like, photoreceptors with ZnO or Cd8 dispersed in a resin binder, etc. 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-8l) as a base material have been proposed in recent years.

a-81 has a so-called dangling bond in which the bond of 8l-8i 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-mentioned defects are compensated for by hydrogen atoms and the dangling bonds are filled in by pressing the button to form an Sl[H bond.

Such amorphous hydrogenated silicon C or less.

a-8l: Referred to as 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 a-8l using the above a-81:H as the base material.
An electrophotographic reproduction machine incorporating a system photoreceptor is shown.
According to this copying machine, a glass IR document mounting table 3 on which a document 2 is placed and a platen cover 4 that covers the document 2 are arranged at the top of a cabinet 1. Below the document table 3, an optical scanning table consisting of a light source 5 and a first mirror unit 7 equipped with 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. The second mirror unit 84°20 is used to keep the optical path length constant.
moves according to the speed of the first mirror unit.

The reflected light from the document table 3 side is reflected by the lens 21. Reflection mirror 8
The light enters the photoreceptor drum 9 as an image carrier in a slit shape through the photosensitive drum 9 as an image carrier.

Around the drum 9, there is a copier charger 10. developer 11,
Transfer section 12. A separating section 13 and a cleaning section 14 are arranged respectively, and each paper feeding roller 16.1 is separated from the paper feeding box 15.
After the toner image is transferred from the drum 9, the toner image is further fixed in the fixing section 19, and then the toner image is ejected to the toner 35. In the fixing section 19, the developed copy paper is passed between a heating p-lar 23 having a built-in heater 22 and a pressure p-lar 24 to perform a fixing operation.

However, as a result of the above-mentioned a-81-81 experience and the inventor's investigation, the following fact was found.

That is, a photoreceptor having an a-8l type substance on its surface.

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 above-mentioned electronic! Ko ρ in true process
discharge (particularly the locations indicated by 10 and 12.13 in Figure 1)
The chemical stability of one surface is poor due to the influence of chemical species generated in the process, and the following defects occur.

(The 11a-8l system layer has a skeleton of bonds between 81 and S1, and the bonding state is relatively good inside the layer, but on the surface side of the layer there are defects (i.e. bond discontinuities) caused by multivalent elements (Sl). In addition, since A-81 is structurally hard, the defects once generated during film formation are retained as they are. Therefore, when used in a device as shown in FIG.

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 unstable electrical and photoconductive properties, phenomena such as one image deletion and white spots (white spots) occur.

That is, FIG. 2(3) shows the surface potential after exposure at the initial stage of copying, but after multiple copies, the initial potential shown by the broken line in FIG. 2(3) becomes as shown by the solid line.

The potential of the non-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 13- charge difference mentioned above in +11.

3) Furthermore, hydrogen is desorbed from the A-8i photoreceptor due to heat and light after manufacturing, which also causes the above-mentioned defects.

(4) Furthermore, the a-8t photoreceptor has poor long-term storage stability due to the above-mentioned reasons, and this must also be resolved 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 corona discharge, ions are formed on the surface of the photoreceptor.

Since no molecules or atoms are adsorbed, the energy band of the photoreceptor is as shown in Figure 3.

However, when various ions activated (or stable) by the flash discharge or ions in the surrounding atmosphere are adsorbed on the surface of the photoreceptor, the impurity level due to this gas adsorption will increase to the surface of the photoreceptor. As a result, the Fermi level (EP) near the surface shifts. However, since the Fermi level near the surface coincides with the Fermi level inside the photoreceptor, a bend (band bending) appears in the energy band in the surface region, as shown in Figure 4, and carrier accumulation occurs due to this band bending. occurs, and a space charge layer is formed. band bending.

From the surface of the photoconductor to the inside (especially when the depth d is 1 μm)
(up to m degrees). Therefore, due to the accumulation phenomenon of carriers based on such gas adsorption and pendency, the electrical conductivity in the creeping direction of the photoreceptor increases significantly.
It is thought that the above-mentioned image deletion occurs. Fifth
The figure shows the lightning, child state density of a light-biting body after adsorption of one gas (E
D is the donor level generated by gas adsorption, EC is the conduction band, and EV is the valence band).

On the other hand, it is known that an electron-accepting or donating substance is adsorbed onto the surface of an a-81 photoreceptor in order to stabilize the surface and control electrical characteristics.

However, since the electron-accepting or donating substance is simply adsorbed on the surface of the photoreceptor, e
It has the drawback that it is easily separated from the same surface during repeated use, and the life of the photoreceptor cannot be extended for a long time.
Moreover, this is because the adsorbed substance is composed of an organic compound and has significantly different properties from inorganic a-81. ! - There is a risk of being exposed.

3. Purpose of the Invention The purpose of the present invention is to stabilize the electrical characteristics of the surface and reduce the surface charge in the creeping (surface) direction, taking into account the above-mentioned special characteristics of photoconductors, especially A-81 photoconductors. I! -Prevention of blurring 1. Preventing image deletion and white spots.

It is an object of the present invention to provide an effective manufacturing method that can satisfy various requirements such as improvement in resolution variation and image density, prevention of changes in image quality due to repeated use, and long-term storage stability of photoreceptors.

4. Structure of the invention and its effects 1. The present invention involves depositing or sputtering a predetermined metal or compound thereof for trapping impurities (for example, adsorbed ions) together with a photoreceptor constituent element (especially silicon) or its compound, The present invention relates to a method for manufacturing a photoreceptor, characterized in that a photoreceptor constituent layer containing the metal and/or its ions is thereby formed.

According to the present invention, the metal atom and/or metal ion-containing layer formed by vapor deposition or sputtering (with 1 empty) has a significant impurity level or trap level due to the inclusion of the metal atom and/or metal ion. It is thought that it is formed near the layer surface due to high concentration change, and for this reason, ions or single atom molecules adsorbed on the photoreceptor surface are trapped by the metal atoms or metal ions mentioned above and are held captive. .

In this case, the band bending described above occurs in the vicinity of one surface due to the formation of an impurity level by the superior metal atom or its ion, as shown in FIG.

The metal atoms or ions thereof cause band bending only to a very shallow depth d'(<<1 μm) from the surface of the photoreceptor (i.e., as shown by the broken line in FIG. 6, as described in FIG. 4). The bending does not extend deep into the interior over a depth d). 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 creeping direction of the photoreceptor, which in turn leads to the formation of a space charge layer. This means that flow etc. can be effectively prevented.

In order to obtain these remarkable effects, it is necessary to use incomplete d as the above-mentioned metal to be incorporated into the I/C in the back protective layer of the a-81 series.
A substance having an ill child shell (deficient in d-orbital electrons) is desirable in that it has the best trapping effect for adsorbed molecules. As such a metal.

Zhou DW Group Urb, Group 1 Vbi-Group II, Group Vtb.

Transition metals belonging to the avnb group, vTIT group, 1b group or 1Tb group may be mentioned, such as Fe, A1. Nl
.

In particular, Fe is f4i1=high. In addition, as metal atoms, the metals that constitute Friedel-Craft catalysts are often used.

AJC/! , , 5h (J6. FeC4, 5nC1!
4, TICJ4.

7 such as Tl1C/, -zrCl, , BF', etc.
Examples include constituent metals of Riede tL and Kura7 catalysts.

According to the method of the Wood invention, when manufacturing a photoreceptor that exhibits the above-mentioned remarkable effects, a metal atom and/or metal ion-containing layer is formed by vapor deposition or sputtering of a metal together with a photoreceptor constituent element or a compound thereof. We should pay attention to the fact that That is.

By applying vapor deposition or sputtering, the target deposition substance (metal-containing substance IFf) can be deposited at high speed,
Productivity improves tremendously. This is because the 'M deposition method and sputtering method physically deposit particles.

In this case, the above-mentioned metal can be supplied using a metal compound as an evaporation source, a gas made of a metal compound, a liquid (a spray-like liquid), a solid ft (a fine-particle solid), etc. It can be supplied in various forms.

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

First, with reference to FIGS. f47 to 10, an example of an a-type electronic photoreceptor manufactured by a method based on the present invention described later will be described.

The prestige 39 in FIG. 7 is a conductive support substrate 41 such as AJ.
It has a structure in which 211 layers of an l-type photoconductive layer 43 made of N-83:H lightly doped with a TIIA group element 1 of the periodic table, such as boron, are formed thereon. 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 electronic EX photoreceptor, and has a good photosensitivity of 1 to light in the visible and infrared regions. In addition, 1 periodic table group ① A element 1, for example, boron, at a flow rate ratio (B, H
6/5ITT4) = 1 to 500 pP to make it intrinsic, that is, I-type (F!11 resistive to I-type)
Q! '～]012Ω-L:nt)L, high resistance can be achieved.

In the longitudinal light body 39, the outermost layer of the photoconductive layer 1ii143 (or its inner vicinity+1) 4 is formed based on the method of the present invention.
It is extremely important that the above-mentioned metal, especially VcFe atomic feathers/or Fs ions, be contained in a predetermined amount in 3a (the region up to the depth indicated by the line f@ in the drawing). These gold I
By containing II or its ion, as mentioned above,
The shadow #ll of the adsorbed substance on the surface of the photoreceptor is made low-frequency,
It is possible to obtain stable characteristics with less change in electrical conductivity in the creeping direction and no image blurring.

For this purpose, it is desirable that the metal content in l143a is 1 to 10,0 OOIF with respect to silicon atoms.

1-The effect is extremely poor in the performance.

Moreover, if it exceeds 10,0 OOP, it is thought that the above-mentioned pan F bending area increases and the photosensitive characteristics are likely to be adversely affected. The metal content is among the
5 to 500 ppm is more desirable.

Further, the thickness of the metal-containing layer 43a is preferably 50x to 2 μm, preferably 50 to 5000x, and 400x to 2 μm.
~2nooX is more desirable.

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

This makes it possible to obtain a photoconductive layer with good photosensitivity, potential retention, and VC.

In addition, in order to sufficiently prevent the injection of electrons from the substrate 41, the upper charge cooking layer 42 must supply an element of Group ⅠA of the periodic table (for example, boron) to a flow rate of B, T(, /St = 50~ 1
It is preferable to dope it with 00.000- to make it a P type (furthermore, f is a P medium type). The thickness of each layer of the photoreceptor described above has a certain range, and the photoconductive layer 42 has a thickness of 2 to 80 μm (preferably 5 to 30 μm), and the blocking layer 42 has a thickness of 100 μm.
It should be ~1 μm (preferably 400-5oooK). If the photoconductive layer 43 has a thickness of less than 2 μm, the charging potential will not be sufficient, if it exceeds 80 μm, it is not practical, and if it exceeds 1 μm, the charge transport ability will be impaired. The hydrogen content in the photoconductive layer 43 is indispensable in order to compensate for dangling bonds and improve photoconductivity and charge retention, and is usually 1 to 40 a.
tomic q6 and 10~a Oatomlc
% is more desirable. Also, Boots Kingli 4
As an impurity to control the conductivity type of 2.

In addition to boron, A1. Ga,
In.

You can use the TI# Periodic Table Group ■A element index.

This blocking layer can also be N-type and tD
t, -hh Kha, P, As, Sb, Bl'!
F17) Can be doped into a group VA photon of the m-phase table.

The photoreceptor in FIG.
:T(fil 44. a-81:H (photoconductive) layer 43
is made up of vR layers sequentially.

, -8IC:T (The layer 44 mainly has the functions of holding potential, transporting charges, and improving adhesion to the substrate 41,
It is preferably formed to have a thickness of μm to 80 μm (more preferably 5 μm to 30 μm). The photoconductor 1943 generates and collects snow conjugates (carriers) in response to light irradiation, and its thickness is 3000X to 5μmc'19.
R~3μm)t is desirable. However, it is preferable that this photoconductive layer is not doped with any impurities such as the above-mentioned poron, since the gear 11a can move smoothly.

In the photoreceptor shown in FIG. 8, the surface cutout 43a of the photoconductor 11430 contains metal in the same manner as described above, and thus the same effects as described above can be obtained.

According to the optical element 9 shown in FIG. 9, compared to the example shown in FIG. 7, amorphous hydrogenated silicon 11 (a-
A metal-containing layer 45a containing the above-mentioned metal is formed in the surface protective layer 45 made of 8IN:H).

By providing the surface retention layer 45, defects in surface characteristics of the a-8t photoreceptor can be overcome.

The interfacial retention Wi layer 45 improves the surface potential characteristics of the a-8I photoconductor, maintains the potential characteristics over the long side, and maintains environmental resistance (humidity and atmosphere). Preventing the influence of seeds) 1. Improved printing durability due to high surface hardness,
It has functions such as improving heat resistance when using a photoreceptor and improving thermal transferability (particularly adhesive transferability), and functions as a surface modification layer.

Moreover, since the above-mentioned metal is contained in this surface protective layer (as layer 45a), the above-mentioned remarkable effects can be exhibited.

In comparison with the example shown in FIG. 8, FIG.
This photoreceptor is formed as a surface-modified layer similar to No. 5, and has metal contained in at least a part of the region 46a as described above. The metal-containing layer 46a can effectively prevent the influence of adsorbed gas while exerting a surface modification effect.

In the photoreceptors illustrated in FIGS. 7 to 1θ, respectively.

As a metal contained in layers 43a, 45a-46a.

In particular, transition metals with incomplete d-electron shells are
The thickness is preferably X or more, but may extend over the entire thickness of the surface protective layers 45 and 46.

In addition, in the example shown in Figure 1M9, the surface modified layer 45 is a-8iC.
:H, the surface modified layer 46 is a-8 in the example of FIG.
They may be formed with IN:H, respectively. The constituent materials of the surface modified layer are not limited to those mentioned above, and examples include a-8iO:H, a-810
:H:F, a-8iO:F. Also,
In Figure 1θ, ! The charge transport layer 44 may be lightly doped with boron or the like.
It is also possible to form a blocking layer 42 as shown in the figure (for example, an a-8IC:H layer heavily doped with boron).

Next, a method for manufacturing the above-mentioned photoreceptor (for example, drum-shaped) and an apparatus therefor (X-vacuum deposition apparatus) will be explained with reference to FIGS. 11 and 12.

A vacuum pump (not shown) is connected to the Pel jar 51 via an exhaust pipe 53 having a butterfly valve 52, thereby causing the inside of the Pel jar 51 to be heated, for example, from 1O-3 to 1O-
A high vacuum state of 7 Torr is maintained, and a hollow drum-shaped base 41 is placed above the Pel jar 51, a heater 55 is built in this drum, and the base 41 is rotatably mounted around a shaft 53 as a rotation axis. There is. The drum base 41 is heated by the heater 55 to a temperature of 150 to 500°C, preferably 250 to 450°C, and the DC power source 4
6 to the drum base 41 KO to -IQ kV, preferably -1 to -6 kV DC negative voltage is applied to the hydrogen gas discharge tube, the outlet of which is connected to the perger 51 so as to face the drum base 41. While introducing active hydrogen and hydrogen ions from 47 into the Pelger 51, the silicon evaporation source 48, the metal compound evaporation source 49, and the aluminum cancer source 51, which are provided to face the drum base 41, are heated and the shutters above each are heated. The aluminum doped a-81:H layer containing a predetermined amount of the metal is formed by simultaneously evaporating silicon, a metal compound, and aluminum by appropriately adjusting the evaporation rate ratio.

When no metal is contained, the metal compound evaporation source 49 is not heated and the upper shutter S is closed.
Form an aluminum doped (I type or P type) a-8i:H layer. a-8IC: To form the H layer, discharge tube 47
While simultaneously introducing hydrogen gas activated by the discharge tube 50 and methane gas activated by the discharge tube 50 into the Pelger 41.

The silicon evaporation source 4B is heated and the upper shutter S is
All you have to do is evaporate A-xysilicon. Note that the evaporation source 4
9 is not used, instead, Fe(Co)@gas is activated and introduced through the release tube 50 by the method described below to form a metal-containing a-8i photoreceptor photosensitive layer based on reaction vapor deposition. You can also.

For example, the structure of the discharge tube 47,50 is shown in FIG. 12, as shown in FIG. A discharge space member 64 made of, for example, cylindrical glass and surrounding the discharge space 63 provided.

It was provided at the other end of this discharge space member 64. The other ring-shaped electrode member 66 has an outlet 65, and the one! By applying a DC or AC voltage between the pole member 62 and the other electrode member 66.

For example, hydrogen gas supplied via the gas port 61 causes a glue discharge in the discharge space 63, whereby active hydrogen consisting of hydrogen atoms or molecules activated by electronic energy and ionized hydrogen ions are transferred to the outlet 6[1]. more excreted. The discharge space member 64 in this illustrated example has a double pipe structure and is configured to allow cooling water to flow through it.
67 and 68 indicate the cooling water inlet and outlet. 69 is a cooling fin for one electrode member 62. The distance between the electrodes in the hydrogen gas discharge tube 47 is 10 to 15 cm, the applied voltage is 600 V, and the pressure in the discharge space 63 is 10 cm.
” It is said to be about i'orr.

FIG. M13 shows a sputtering apparatus 70 for forming a metal-containing photoreceptor constituent layer according to the present invention.

According to this sputtering apparatus, a hollow drum-shaped substrate 41 is rotatably arranged in a vacuum chamber 72 separated by a vessel wall 71,
A heater 83 is built in this drum. A silicon target 76 is attached to a target support member 75 provided at a position facing the tram base 41. The silicon target is non-doped amorphous silicon with a purity of 9N or higher. The inside of the vacuum chamber 72 is evacuated to a high vacuum of I x 10-' Torr or less by the exhaust pump 77, and the drum base 41 is heated to a temperature of 1
00 to 300' (preferably 150 to 250°C.) Next, the pulp 78 is opened and an inert gas Ar73 is added as a wI bombarding ion source during sputtering, and the pulp 79 is opened and H774 or CH is added as a reactive gas. , etc. 75.Furthermore, when necessary, 80 is opened to introduce the monometallic compound 88 into the vacuum chamber 72. Note that 84 is a mixing chamber for mixing Ar and other reaction gases.Introduced into the vacuum chamber 72 The mixed gas was adjusted by Pargua 7 and was heated to 1×I Q-s-I
Maintain back pressure. I Mllz~50 generated by the high frequency power source 81K on the target support member 75
A high frequency wave of Mllz is applied and, on the other hand, a 7-phase is taken through the rotation axis of the base 41.

Alternatively, -sputtering is performed by applying a negative DC voltage of 50 to 500 ports. The temperature of the drum base 41 is measured by a thermocouple 85 and a temperature controller 86.
is maintained by adjusting the

In the above manufacturing method, to form the Fe-containing layer, Fe compound soot may be supplied from the supply source 88, and this supply mechanism is configured as shown in FIG. 14, for example. In other words, liquid pentacarbonyl iron (Fe(Co)s) indicated by 98 is stored in a cylinder 93 as a supply source, and at this turn, Ar gas 99 is blown in at an adjusted flow rate to cause bubbling, whereby Ar is Fa(Go)s gas 88 as a carrier gas is introduced into the above-mentioned sputtering apparatus through a flow needle 97. In this case, F in Ponbe 93
The vapor pressure of e(Co)s may be, for example, 34 Torr, and the liquid temperature may be 25°C. 90 in the figure is each flow rate eA regulating valve.

The above Fe(Co)e gas is decomposed by discharge together with other reactive gases in the sputtering equipment, and the resulting or 45
a, 46a) is formed. Therefore, a-81:H (or a-8tN:H) under Fe-free conditions.

By introducing Fe(Co)s as described above at the final stage after depositing a-8iC:H) to a predetermined thickness, it can be formed easily and accurately.

In addition, when forming the above a-8t film, in order to compensate for dangling bonds, fluorine is introduced in the form of 5IF4 or the like instead of the above-mentioned H or in combination with H.
a-81:F, a-81:H:F, a-8IN:
F, t-8IN:H:F, a-8IC:F, a-8I
It can also be set as C:H:F. In this case, the amount of fluorine is 0.01 to 20 atomic%.
10 atomic units are more desirable.

In addition, in the above method, F is used to supply Fe.
Although e(Co)s gas was used, other Fe supply methods may be employed. For example, fine particulate Fe compounds (eg fersene) or atomized Fe compounds (eg pentacarbonyl iron) can be introduced into the gas release device.

Next, one embodiment of the present invention will be described with reference to a specific embodiment.

Example 1 Drama shape A was formed by vacuum evaporation method (Figures 11 and 12)
An electrophotographic photoreceptor having the structure shown in FIG. 7 was fabricated on a J substrate.

First, a support with a smooth surface (surface roughness 0.2
8) After washing the surface of the drum-shaped AJ substrate with trickle ethylene, acetone, and pure water, it was placed in a Pelger with an internal pressure of 10-6 Torr.
The temperature of the substrate is evacuated at a temperature of K11 so that the temperature is 1.r, and the substrate is heated and maintained at a predetermined temperature of 1, for example, 400°C.

A P-type aluminum-doped a-81:H layer having a charge blocking function was formed into a 1 μm thick JJ film at a deposition rate of 1101 t/hr under the following conditions.

H, flow fl 50 cc / a + u4 Evaporation source Polycrystalline silicon (evaporated by electron gun heating) Aluminum (evaporated by resistance heating method) Evaporation amount ratio S l /AJ = 1 / 1.5 X 10
-'Discharge tube DC discharge tube (discharge power 350W) Substrate voltage -5kV Next, in the same device, the evaporation amount ratio of 81 and Al is 1:
After forming a 15 μm thick ■-shaped aluminum doped a-8i:H layer under 5×10′ conditions (others being the same as above),
Fe metal is evaporated using an electron gun heating method, and the evaporation amount ratio is 81.
:AJ :Fe=1 : 5X 10-' : 7.5
A layer containing Fe with a thickness of 2000X was further provided as X10-5 to complete an electrophotographic photoreceptor.

Using this photoreceptor, images were produced using a copying machine (a modified U-Bix 3000 machine manufactured by Konishiroku Photo Industry Co., Ltd.), and the results showed that the resolution was good in one gradation, and the loss in one image was high. No clear images were obtained.

Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

Comparative example 1 Effect of the Fe-containing layer in the layer structure in Example 1.

In other words, the purpose was to clarify high-quality image formation by maintaining stable potential characteristics and surface chemical stability.

A photoreceptor without a Fe-containing layer was prepared and one image evaluation was performed. As a result, one image was washed out, there were many white spots on one image, and only an image with poor resolution was obtained.

Example 2 Layered structure using the same manufacturing method as Example 1, that is, drum-shaped AI! A 1 μm thick P-type a-8i:H charge pushing layer and a 15 μm thick aluminum lightly doped a-8lCH layer were formed on the support, and then a 1 μm thick aluminum light doped a-8lCH layer was formed.
a- containing 000X metal or non-metal additives
81: A photoreceptor having a laminated H layer was produced. As a metal or non-metal additive, Fe-Co-N1. Zn,
AA'- and F, (J) The above additives are made by heating the following metals or gaseous elements in an evaporation source 49 or in a discharge tube 5.
The a-8l:H layer contained the a-8l:H layer through discharge decomposition.

Fe metal (electron gun heating) Co gold l1g (〃) Nl metal (〃) Zn gold M (resistance heating) AA! Metal (resistance heating) Fluorine (F,) gas (DCC10 Chlorine (CJt) gas (I)C discharge) Using each drum made in this way, a copying machine (U
-Bix 3000 modified machine: Konishiroku Photo Industry C Co., Ltd.) [)
The results of comparing the image quality after 100,000 consecutive copies and the light attenuation characteristics of the photoreceptor (half-exposure f
E%) is shown below.

In the above table, ◎ dihedral image has good resolution of 1 gradation, m image density is high and clear.

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

62 Occurs partially on image.

X: Occurs in an area of 50 inches or more on the image.

Example 3 An electrophotographic photoreceptor having the structure shown in Figure 8 was fabricated on a drum-shaped AI substrate by a sputtering method (Figure 13).

First, the support, for example, a smooth surface (surface roughness 0.2
After washing the surface of the drum-shaped AJ substrate with 8) in the order of 1 chloroethylene, acetone, and pure water, it was placed in a vacuum chamber and rotated at a rotation speed of 26 rpm. A silicon target was attached to a target support member, the inside of the vacuum chamber was evacuated to a high vacuum of 10-'TorrO using an exhaust pump, and the drum base was heated to a temperature of 200°C using a heater.

Next, Ar gas, Hz gas, and CH gas were introduced at a flow rate ratio of 5:1:5, and the back pressure of the vacuum chamber was set to 5 × 10−”.
Torr, frequency 13.56 to silicon target
■Sputtering by applying high frequency power of 2-ii
An a-ale:H layer having a cargo transport function was formed to a thickness of 15 μm at a deposition rate of 3 μm/hr.

Subsequently, the supply of CH4 gas was stopped, Ar gas was introduced, sputtering was performed, and an undoped a-
81:i (after forming the charge generation layer, Ar gas-v-f
+ Bubble the liquid of LiDOllrφ・誹AIKIST＾桡塼匡しきすARCRSOSO+rubonyl iron Fe(CO), and introduce Fa(Co)s into the vacuum chamber using -Ar gas as a carrier. .

Sputtered with a mixed gas of Ar and
An electrophotographic photoreceptor was completed by further providing a layer containing 000 x Fa. using this photoreceptor.

Images were produced using a copying machine (U-Bbc 3000 modified machine, manufactured by Shoseiroku Photo Industry Co., Ltd.), and as a result, there was no blurring of the image, no white spots on the image, and good resolution and gradation. Clear images with high 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 photoconductor having a functionally separated layer structure in Example 3, F
In order to clarify the effect of the Fe-containing layer, that is, high-quality image formation due to stable potential characteristics and maintaining the chemical stability of the surface, a photoreceptor without the Fe-containing layer was prepared and one image evaluation was performed. As a result, one image was deleted, there were many white spots on the image, and only an image with poor resolution was obtained.

*F by the Mq 4 sputtering method with the layer structure in Example 3.
rtc, -yx other than Fe(Co)s regarding e content.

psenFe (CB Hl)! and hexaphcjμ
A photoreceptor was produced using iron acetylacetonate (HFA)a as a Fe supply source. Fersen and hexafu-7cetylacetotetrairon 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.
Fe was contained in the a-8l:H layer by sputtering with a mixed gas of Ar+Hg.

When images were produced using these photoreceptors +
As in the case of Fe (co), a clear image was obtained with no image loss or white areas. Further, even after repeated copying 200,000 times, stable and high quality images were continuously obtained.

[Brief explanation of drawings]

FIGS. m1 to 5 show conventional examples, and FIG. 1 is a schematic sectional view of a conventional electrophotographic copying machine. (2nd round included) and ■) are graphs showing changes in surface potential of the A-81 series photoreceptor after exposure. Figure 3 is an energy band diagram of the photoreceptor before gas adsorption. Figure 4 is an energy band diagram after gas adsorption. FIG. 5 is a diagram showing the density of electronic states. It is. 6 to 14 show embodiments of the present invention. Figure 6 is an energy band diagram of the photoreceptor. FIG. 7, FIG. 8, FIG. 9, and FIG. 10 are sectional views of each a-8t type photoreceptor. FIG. 11 is a schematic sectional view of a vacuum evaporation apparatus, and FIG. 12 is a sectional view of a gas discharge tube. FIG. 13 is a schematic cross-sectional view of the sputtering apparatus. FIG. 14 is a schematic cross-sectional view of the Fe compound gas supply source. In addition, in the code shown in 1 drawing - 39・----1--・----1-------a-8i
System photoreceptor 41=--------Support (substrate) 42--Plucking layer 43
・−・−・−・−−〜−−Photoconductive layer 44−=−−1−−
−−−−−・−Charge transport layer 45.46・−・−11−
---Surface modification N (surface protective layer) 43a, 45a, 46
th ----1・-Metal stand・Layered 47.50--
・・・・−1−−−Gas discharge tube 4B, 49.51−
---- Evaporation source 70 ---------- Sputtering device 76 = ---- - - - - - - - - - One target. Representative Patent Attorney Hiroshi Aisaka (and 1 other person) Fig. 3 Fr Fig. 4 Fr Fig. 5 Iden J-Joryu 7th degree N (E) Fig. 6 Fig. 7 Fig. 8g 39 No. 9v! i Fig. 12 Fig. 14 Suha 9 ivy tatami mats

Claims (1)

[Claims] l. A photoconductor constituent layer containing the metal and/or its ions by vapor-depositing or sputtering a predetermined metal or its compound for impurity trapping together with the photoconductor constituent element or its compound; A method for manufacturing a photoreceptor, the method comprising: forming a photoreceptor. A transition metal belonging to the nb group is used. A method according to claim 1. 3. As the metal, a metal constituting a Friedel-Craft catalyst is used. A method according to claim 1. 4. The metal and/or its ion-containing cap is 1-10,0 OOP with respect to the silicon atoms constituting the photoreceptor. The method described in any one of claims 1JJ4 to 3. 5. Photoreceptor structure containing metal and/or its ions. The layer is formed as the outermost surface layer of the photoreceptor or a layer near the inner surface thereof. The method described in any one of claims 1 to 4. 6. The photoconductor constituent layer containing metal atoms and/or ions thereof may be made of amorphous hydrogenated and/or fluorinated silicon, amorphous hydrogenated and/or fluorinated silicon carbide, amorphous hydrogenated and/or fluorinated silicon nitride, Alternatively, it may be formed from amorphous hydrogenated and/or fluorinated silicon oxide. A method according to any one of claims 1 to 5. 7. The thickness of the photoreceptor constituent layer containing metal atoms and/or their ions is 50x to 2 μm. A method according to any one of claims 1 to 6.