JPS6029755A - Photoconductive member - Google Patents

Abstract

PURPOSE:To prevent deterioration of photosensitive characteristics and filming of a developer by laminating a blocking layer, a photoconductive layer composed essentially of silicon and contg. H on a conductive substrate and having a smooth surface, and a surface coating layer in succession to form a photoconductive member. CONSTITUTION:A blocking layer 2 for preventing injection of charge from a conductive substrate 1, a photoconductive layer 3 composed essentially of silicon and contg. H and having a smoothed surface, and a surface coating layer 4 are laminated in succession on the conductive substrate 1 to form a photoconductive member. The layers 2, 3 are each composed essentially of silicon and contg. H, and the layer 3 is smoothed on the surface by glow discharging a material gas contg. at least F in the process of forming the layer 3. Or before the layer 4 is laminated, the layer 3 is smoothed on the surface by mechanical polishing. As a result, the protuberances of a-Si generated once is etched with F radicals and smoothed, and further polished by mechanical working. Since the layer 4 is finished smoothly, it can prevent deterioration of photosensitive characteristics caused by repeated uses, and also filming of a developer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a photoconductive member applied to electrophotographic photoreceptors and the like.

[Technical backbone of the invention and its problems] Electrophotographic photoreceptor 1. Regarding photoconductive materials used in solid-state W1a elements, Nagano Mei is an amorphous material that has a photosensitive wavelength range extending to longer wavelengths than selenium, etc., and is non-polluting, does not require recovery, and can easily be made into a large area. Amorphous silicon (hereinafter also referred to as amorphous silicon or a-8i) is attracting attention.

A-8i can also be manufactured by sputtering using polycrystalline silicon as a target, but usually Si
It is manufactured by a glow discharge method in which raw material gas containing silicon atoms, such as Ha, is decomposed by glow discharge. The amorphous silicon produced in this way contains a large amount of hydrogen in the silicon network, and this hydrogen serves to compensate for the dangling bonds of the silicon. But still? Since units exist at a fairly high density in the band gap due to the inability to compensate for Ii or the presence of bonds such as 5IH2, the specific resistance in the dark is small. That is, the conduction band
There are many thermally excited electrons inside. When such a device is used in an electrophotographic photoreceptor, etc., there is a problem that the surface charge generated by corona fi-electricity is canceled out by the excited electrons and is not retained until development. k.

For this reason, in the past, a blocking layer was provided between the conductive substrate and the amorphous silicon layer to prevent injection of electrons or holes from the photoconductive substrate. This blocking store has a very high resistance and inhibits the flow of charges, or is a semiconductor called P-type or N-type, which has many acceptor units and donor levels in the gap and allows electrons or holes to flow. It is formed by something that traps 17M. Furthermore, in order to stabilize the photoconductive layer, a surface coating layer is provided on its surface.

This surface TR layer should be made of a material with high resistivity and high light transmittance, but if it floats, it will have difficulty handling charges and absorb light, resulting in a high residual potential and poor photosensitivity. Therefore, the thickness of the surface P1 covering layer was usually about several hundred h to several thousand amps.

By the way, a-3i manufactured by the glow discharge method
grows abnormally due to irregularities and irregularities on the surface of the electrocardial substrate,
Hemispherical protrusions are formed on the surface of the photoconductive layer. However, these protrusions are usually about 0.5 .mu.II to 5 .mu.m thick, and the thickness of the surface coating layer is larger than this. Because of this, is the photoconductive layer uniform? l! ! There is a problem in that the photosensitive characteristics deteriorate with repeated use without proper cleaning, and additionally, excess developer adheres to defective portions of the surface coating layer, making it easy to cause developer filming.

[Object of the Invention] The present invention has been made based on the above-mentioned circumstances, and its purpose is to prevent the deterioration of photosensitive characteristics due to repeated use, and to easily prevent the filming phenomenon of the developer. It is an object of the present invention to provide a photoconductive member that can prevent this from occurring.

[Summary of the Invention] In order to achieve the above object, the present invention includes a blocking n that is provided on a conductive substrate and prevents charge injection from the conductive substrate, and a silicon atom containing hydrogen as a base material and having a surface containing hydrogen. A photoconductive member is obtained by sequentially laminating a smoothed photoconductive layer and a surface coating layer.

[Embodiments of the Invention] Examples of the present invention will be described below with reference to the drawings.

FIG. 1 is a sectional view showing a photoconductive member according to a first embodiment of the present invention. In the figure, the reference numeral 1 is a 6911 base, which is formed of, for example, an aluminum flat plate or an aluminum drum. The surface of this conductive substrate 1 is provided with blocking to prevent charge injection from this 1s conductive substrate 1! ! ! 2 is provided, for example, by glow discharge decomposition of a raw material gas that is a mixture of B2He gas and 5iHi gas, or by oxidation of the y9 conductive substrate 1 (thus, it is formed. Furthermore, on the surface of the blocking layer 2, is provided with a photoconductive@layer 3 whose surface is smooth and contains hydrogen using silicon atoms as a matrix, and is formed by glow discharge decomposition of a raw material gas that is a mixture of B21-16 gas and 5iHa gas, for example. The first photoconductive F?3'A and a raw material gas containing at least a fluorine atom, which is a mixture of SiH4 gas and 81F4 gas, are decomposed by glow discharge and are then deposited on the first photoconductive opening 3A. For example, a transparent surface coating layer 4 is provided on the surface of the photoconductive layer 3, and a transparent surface coating layer 4 is formed by, for example, 5iHa gas and CHa gas. It is formed by glow discharge decomposition of a mixed raw material gas.

The photoconductive member described above can be manufactured, for example, by a manufacturing apparatus shown in FIG. This manufacturing apparatus includes a reaction vessel 12
It has a gas supply section 14 and an exhaust device (not shown). A conductive substrate 1 (for example, a mirror-polished 150+ nm x 200 mm aluminum plate) can be placed inside the reaction vessel 12, and the conductive substrate 1 is heated to a predetermined temperature, for example, 100 to 400°C. A support body 20 having a heater 18 is provided, and an electrode 24 is provided above and facing the support body 20 and having a large number of gas blowing holes 22. Electrode 24
A high frequency power source 28 (for example, 13.56 MH2) is electrically connected to the support member 20 and the support body 20 via a self-help matching membrane 26 so that a high frequency electric field can be generated between the two. Further, the electrode 24 as a whole also serves as a gas blowing device, and can blow out the gas supplied from the gas supply section 14 between the electrode 24 and the conductive substrate 1 . therefore,? ! ! When a high frequency electric field is applied between the electrode 24 and the conductive substrate 1 while blowing out the gas, plasma gas excited by glow discharge can be generated. Note that the electrode 24 is provided with an insulator 30.3 with respect to the reaction vessel 12 and the gas supply section 14.
It is electrically insulated by 2.

Further, the reaction vessel 12 is connected to an exhaust device (not shown) via a gas flow fitting 33 that controls the flow rate of gas exhausted from the reaction vessel 112 by 1 g. The gas supply unit 14 includes, for example, a 5iHa gas cylinder 34 charged with a gas containing hydrogen using at least silicon atoms as a host, such as Si He gas (or 5i21-1s gas), and a B2 H6 gas cylinder 35 filled with Bz He gas. A CHe gas cylinder 36 filled with CHe gas and a 3i F gas filled with a gas containing at least fluorine atoms, for example, 5iFa gas.
4 gas cylinder 37, a CF4 gas cylinder 38 filled with a gas containing at least fluorine atoms, for example, CF4 gas, and a valve 39 attached to each gas cylinder, and supplies various gases arbitrarily into the reaction vessel 12. It is designed so that you can

When manufacturing the optical wj electrical member shown in FIG. 1 using the manufacturing apparatus shown in FIG.
The inside of the reaction vessel 12 is made into a vacuum of 10'3 to 10' torr using
Maintain at 00°C. Convert the B2 He gas in the Bz He gas cylinder 35 to the 5iH gas in the 81H4 gas cylinder 34.
The mixture is mixed with a gas at a flow rate of about 10-4 to 10'2 and supplied into the reaction vessel 12, and the n thickness is 0.2 to 2.5 μI1.
A blocking gate of about 1 is formed by glow discharge decomposition.

Next, the B2 He gas in the 82 H1l gas cylinder 35 is mixed with the Si He gas in the 5IHa gas cylinder 34 at a flow blue ratio of about 104 to 10-2, and the mixture is decomposed by glow discharge while being supplied into the reaction vessel 12. ''A first photoconductive layer 38 having a thickness of about I2 μm is formed. Note that this first photoconductive ff13A consisting of a-3i grows abnormally due to irregularities, deafness, etc. on the surface of the conductive substrate 1, etc., and the first photoconductive l
A hemispherical protrusion will be formed on the surface of N5A. The Si Fa gas in the l5iFa gas cylinder 37 is
10% for 5iHa gas in He gas cylinder 34
While mixing and supplying the mixture into the reaction vessel 12, glow discharge decomposition takes place for about 5 to 10 minutes. ! A jff2 photoconductive n3B having a thickness of about 0.5 to 1.0 μm is formed. When this second photocardiographic gate 3B is formed, the first photocardiographic gate 3
Even if the surface of A is uneven, a-8i is deposited on it one after another, and at the same time, the protrusions on the surface of a-81 that have undergone HI are etched, so that the surface of the second photoconductor 3B is Smoothed, the first photoelectric property 1ffi3A and the second photopolytic property f
As a result, the surface of the photoconductive W33 consisting of f13B is smoothed. Generally speaking, the mechanism of surface smoothing is that the deposition mechanism of a-3i is that hydrogen radicals generated by glow discharge strip off hydrogen bonded to silicon near the surface of the formed film, and the next deposition occurs. Therefore, if fluorine radicals, which are much more active in repelling hydrogen radicals, exist, this reaction will be further promoted, and since fluorine radicals also etch silicon, deposition and etching will occur when forming the a-8i film. They occur at the same time. Therefore 5iH
When a film is formed by mixing a gas containing fluorine into a gas (or 3128s gas), the deposited protrusions on the i surface are etched, and the etched surface is further etched with a.
-8i is deposited, resulting in a photoconductive β with a smooth surface. Note that Il! of this second photoconductive layer 3B! As mentioned above, the best thickness is about 0.5 to 1.0 μm, and if it is too loose, the photosensitivity will deteriorate. In this way, the photoconductivity is 1! After J3 is formed, the CF-It gas in the CHa gas cylinder 36 is mixed with the 5iHa gas in the 3i Ha gas cylinder 34.
Mix twice and leave in the reaction vessel 12 for glow discharge decomposition, a/! Is the iI on the order of hundreds to thousands? ! ! !
Overturning 4 is formed. This surface wave mFff4 becomes an a-8i port containing carbon. In addition, the above blocking tang 2,
Photoconductive housing 3 and surface wave I? JFl! 14 to reaction vessel 1
2, the pressure inside the reaction vessel 12 is set to 0.
The exhaust speed of the exhaust system was adjusted to about 1 to 1.0 torr to maintain a steady state.

In the photoconductive member manufactured in this manner, since the surface of the photoconductive layer 3 is smooth as described above, the surface formed thereon is smooth. LMlffi 4 can maintain good photosensitivity and its surface is uniform even when the film thickness is from several hundred to several thousand.

Using a photoconductive member that had been subjected to such smoothing treatment, the charging, exposure, and development cycles were repeated and the changes in its properties were investigated. As a result, the initial charging capacity of the photoconductive member that had not been subjected to the smoothing treatment was 500 at a charge of 0.4μC/c1
The surface potential of the photoconductive material that had been smoothed decreased to about 300 V after turning the rod about 50 times, whereas the surface potential of the photoconductive material that had been smoothed decreased to about 300 V.
The surface potential is 550V, which is slightly Q, and it can be charged 100,000 times.
There is no deterioration of the photosensitive characteristics even during the green cycle of exposure and development cycles, and developer filming development is less likely to occur even after 100,000 cycles of II! ii. After image formation, a good image after image formation could be obtained.

Next, other embodiments will be described. FIG. 3 is a sectional view showing a photoconductive member according to a second embodiment of the present invention. 1st
Components that are the same as those shown in the figures are designated by the same reference numerals, and detailed explanation thereof will be omitted.
The photoconductive material 53 formed on the surface of , which contains hydrogen and has a smoothed surface using silicon atoms as the host, is treated as follows.
It was composed of That is, 82F-1s gas and 5IH
The raw material gas mixed with t gas is glow discharged m and a-
81 gates are formed, and then a glow discharge is generated using a gas containing fluorine such as SiFa or CFL.
The protrusions on the front surface of -3i are etched by the fluorine radicals generated by this glow discharge to form a photoconductive layer 3 with a smooth surface.

Such a photoelectric member can also be manufactured by the manufacturing method shown in FIG. StFa gas in the gas tank 37 or CF in the cFa gas tank 38
& Gas will be used.

Note that in the first case of this embodiment, unlike the case of the first actual M example,
Since SiF4 gas or CFaF2 gas 3i)in gas is not mixed, only the protrusions on the a-8i surface are etched, and no new a-3i is deposited.

The photoconductive member manufactured in this way also exhibits optical 1717 properties.
! Since t3 was smoothed, it was possible to obtain the same experimental results as with the photoconductive member described in the first example.

It goes without saying that the above-mentioned embodiment is merely an example, and that various modifications can be made within the scope of the gist of the present invention.

For example, in both embodiments, the photoconductor layer, the photoconductor layer, and the surface coating layer were constructed using a-3i as a penis, but the number of layers is small (it is only necessary that only the photoconductor layer has Si atoms as its matrix), and Smoothening of the photoconductive surface is not limited to the etching effect of fluorine radicals as explained in the above examples, but can also be achieved by lapping with a lapping agent or by using a special abrasive. The surface may be smoothed by mechanical polishing, such as polishing. However, electric discharge machining cannot be used because the surface becomes rough.

[Effects of the Invention] As is clear from the above description, in the photoconductive member of the present invention, since the surface 71 covering layer is stacked on the photoconductive layer having a smooth surface, its outer surface is smooth. It has excellent effects such as being uniform, preventing deterioration of photosensitive characteristics due to repeated use, and preventing developer filming from easily occurring.
It is something that

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a photoconductive member according to a first embodiment of the present invention, FIG. 2 is a schematic explanatory diagram showing an example of a photoconductive member manufacturing apparatus, and FIG. 3 is a second embodiment of the present invention. FIG. 2 is a cross-sectional view of an example photoconductive member. DESCRIPTION OF SYMBOLS 1... Conductive substrate, 2... 10 packing layer, 3... Photoconductive layer, 4... Surface pull-back Figure 1, Figure 3 figure

Claims (1)

[Claims] (1) A blocking layer that is provided on a conductive substrate and prevents charge injection from the conductive substrate, and a photoconductive layer that is made of silicon atoms and contains hydrogen and has a smooth surface. A photoconductive member characterized in that the layer and the surface wave W1n are successively ff1li(). Electrically conductive member. (3) The surface coating layer includes silicon atoms as a host and contains hydrogen. (4) The photoconductive layer includes at least The photoconductive member according to claim 1, wherein the surface of the photoconductive member is smoothed by glow discharge decomposition of a raw material gas containing fluorine atoms. (5) The photoconductive layer is formed by laminating a surface coating layer. 2. A photoconductive member as claimed in claim 1, wherein the surface has previously been smoothed by mechanical polishing.