JPS63255374A - Production of electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To form high quality films for electrophotographic sensitive bodies at high speed when Si films are formed on the surfaces of base bodies with gaseous starting material such as silane and electron cyclotron resonance sources, by arranging the resonance sources each having a rectangular prism- shaped resonance chamber around the base bodies. CONSTITUTION:When photosensitive layers of Si as a photoconductive material are formed on the surfaces of base bodies with gaseous starting material such as SiH4 or Si2H6 and electron cyclotron resonance (ECR) sources to produce electrophotographic sensitive bodies, resonators 13 as the ECR sources are arranged around a cylindrical film forming vessel 11 within a range of >=30 deg. on both sides of a perpendicular plane along the central axis of the vessel 11. Microwaves are introduced into the resonators 13 from the inlets 17 and the gaseous stating material such as SiH4 is fed from introduction pipes 20 through distribution pipes 21. The gaseous SiH4 is excited by the microwaves and enters the vessel 11 through connection holes 19. High quality films for the sensitive bodies are formed on the base bodies on shafts 12 at high speed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing an electrophotographic photoreceptor having a photosensitive layer made of a photoconductive material using a hydrogen-silicon compound as a base material.

[Conventional technology]

Electrostatic copying machines and printers have traditionally used Se, Se/Te, As, Ses, CdS, and Zn as photoreceptor materials for electrophotographic methods such as the Carlson method.
Inorganic photoconductive materials such as O and organic materials such as PVK-TNF have been used. These various materials each have characteristics as a photoreceptor, but they lack rigidity and sensitivity. Furthermore, it has drawbacks such as toxicity, and it cannot be said that it fully satisfies the characteristics required of a photoreceptor.

In contrast, amorphous silicon (a-3i) materials have been commercialized in part because they have excellent rigidity and heat resistance, and have little impact on environmental pollution.a-S
Although i-type photoreceptors have many characteristics superior to conventional photoreceptors, they are currently much more expensive.

This means that a mass production method suitable for mass production or high-mix low-volume production has not been established for the various methods conventionally known as methods for producing A-3T photosensitive materials, such as glow discharge, sputtering, and photo-CVD. It is shown that.

The conditions necessary for reducing costs are increasing the deposition rate,
Although it is a mass production method, in order to increase the film formation speed, silane (siH4) and disilane (Si.

It is necessary to increase the density of excited species in the raw material gas such as H&).

For this purpose, in addition to glow discharge using frequencies ranging from direct current to radio frequencies, which have been conventionally used, film-forming methods using microwaves with even higher frequencies have also been attempted. There is also an electron cyclotron resonance source (ECR) method that adds . However, these methods also have many problems in terms of film formation speed and mass production system.

FIG. 7 shows a principle diagram of an EAR film forming apparatus, in which a plasma chamber 1 has a microwave introduction section 2) a gas introduction section 3, a magnetic coil 4, and an outlet 5. The film chamber 6 includes a raw material gas introduction section 7, a substrate holder 8, and an exhaust port 9. A microwave of, for example, 2.45 GHz is introduced from the microwave introduction part 2 of the plasma chamber L, and excited gases such as H, N, rare gas, etc. are introduced from the gas introduction part 3, and the ECR conditions are satisfied. Let the discharge occur.

In this case, if the microwave frequency is 2.45 GH2, the magnetic flux density is 875 gauss, which satisfies the ECR conditions.

The film forming chamber 6 is evacuated by an exhaust pump connected to an exhaust port 9, and 5iHa of the film forming raw material gas is introduced from the raw material gas inlet 7. This raw material gas comes into contact with the excited gas excited in the plasma chamber 1 and becomes active, so that film formation on the substrate holder 8 progresses.

The substrate is heated to 100 to 300°C if necessary.

Note that in the above example, an electromagnet is used to apply a magnetic field to the plasma chamber l, but a permanent magnet may also be used.

The film forming method described above has the following drawbacks.

First, the plasma chamber of the ECR method is prone to generating electrical discharge (
In order to do this, one or more specific constant pressure waves are designed to occur. Therefore, it is difficult to increase the size of the plasma chamber to 1 to 2 m so as to be suitable for mass production of photoreceptors, and there is a lack of expandability in the film forming area.

Second, since the raw material gas is not directly exposed to the plasma, it is indirectly excited, and the efficiency is not good. In other words, the deposition rate is not as high as expected from the increase in plasma density, and is at most 10 IIm/hr. , which is equivalent to the maximum value of a normal glow discharge.

Thirdly, film forming methods such as glow discharge, sputtering, and microwave can also be used to form films at high speeds of 20 am/hr or more if many quality requirements for photoreceptors are ignored; When high-speed film formation is performed, the film quality becomes non-uniform, and abnormal growth areas such as film protrusions are likely to occur, increasing defects on images. The same is true for the ECR method, and unless appropriate conditions are set, quality problems will occur.

[Problem that the invention seeks to solve]

In view of the drawbacks of conventional film forming methods as described above, the present invention provides a method for manufacturing a photoreceptor having a photosensitive layer made of a photoconductive material with hydrogen-silicon as a base material at high speed and with high quality. The purpose is to

Means for Solving Problem C] According to the invention, this object is achieved by forming the photosensitive layer using an electron cyclotron resonance source with a rectangular parallelepiped-shaped resonant chamber.

[Effect]

In the present invention, the substrate has a rectangular parallelepiped resonance chamber and faces a densely arranged electron cyclotron resonance source, and is exposed to a film-forming source gas that is directly excited by the electron cyclotron resonance source to form a film. be exposed.

(Example〕 Next, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 schematically shows the structure of a film forming furnace used in the method of the present invention. A plurality of shafts 12 are arranged in a cylindrical film forming container 11, and these shafts 12 have a length, for example. It was selected to have a size of approximately 2000 mm and a diameter of 80 am, and is able to rotate and revolve as shown by the arrow.A heating means such as a heater is installed inside it, and a cylindrical aluminum base is installed on the outside. It is installed.

A resonator 1 serving as an ECR source is installed around the furnace wall of the film forming container 11.
A plurality of resonators 3 are attached, and each resonator 13 is connected to a waveguide 14 which is a microwave supply path. Each resonator 13 has a rectangular parallelepiped-shaped resonance chamber. Although not shown in the figure, an exhaust pump for exhausting the film-forming source gas is attached to the film-forming container 11.

FIGS. 2 and 3 show the arrangement of the ECR sources when viewed in the axial direction of the film-forming container 11. In the example of FIG. While the source resonators 13 are arranged, in the example shown in Fig. 3, they are arranged parallel to the axial direction of the film-forming container and alternately in the circumferential direction, ensuring uniform film-forming distribution on the substrate. You can improve your sexuality.

In either arrangement, the resonator 13 of each ECR source
Since the resonance chamber is formed in the shape of a rectangular parallelepiped, the ECR sources can be arranged densely, and a uniform film can be formed over a large area. In the figure, numeral 15 is a drive/exhaust system.

FIG. 4 shows details of the ECR source, in which a resonator 13 is surrounded by a magnetic coil 16, and a microwave inlet 17.
There is a seal window to block the atmosphere, and there is a raw material gas introduction pipe and a gas distribution pipe 21 near the film forming container connection port 19.
are provided, forming an internal plasma chamber 22.

If the resonator 13 as an ECR is not placed within a predetermined angle θ from a vertical line passing through the center of the film forming container 11 as shown in FIG. This prevents the particles from falling onto the shaft 12 to which the substrate is attached, and the surface quality of the photoreceptor is improved. The angle θ is approximately 30°.

Next, a method for forming a film using the above film forming furnace will be described.

In order to form a film, the current supplied to the magnetic coil is determined by lj!
ff to a value that satisfies the ECR conditions, microwaves are introduced from the microwave inlet 17, and a gas containing silicon, which is a raw material gas for film formation, such as monosilane (SiH4), disilane (StgH4), is introduced from the raw material gas introduction pipe 20. When the source gas is supplied, the source gas is guided into the resonator 13 through the gas distribution pipe 21, excited by microwaves there, and enters the film forming container 11 to form a silicon film on the substrate on the shaft 12. In this case, by directly supplying the source gas into the resonator 13, which is the ECR source, the film formation rate can be dramatically improved. That is, according to the conventional method,
Resonator 13. There is only a gas introduction pipe 23 for supplying gas such as hydrogen and rare gas (halogen gas), and raw material gas for film formation is supplied into the film formation furnace. Now, for example, 30cc of H2 gas is supplied from the gas introduction pipe, and Si is deposited in the film forming furnace.
Supply 20cc of H, microwave frequency 2.45GH
z, film formation speed 7μ when film was formed under the conditions of microwave power 400W, substrate temperature 180°C, gas pressure 5mTorr
m/hr. On the other hand, under the same conditions, S i Ha
When only the gas is supplied from the raw material gas introduction pipe 20 and the gas is not supplied from the gas introduction pipe 23, the film forming rate is 1.
It reached 5μm/hr.

The gas pressure during film formation is important in improving the surface quality of the photoreceptor, and at 100 mTorr or more, there is a high probability of collision between gas molecules, and undecomposed powder is generated, resulting in a decrease in surface quality.

Further, in order to form a film under conditions where collisions of gas molecules are small, it is preferable that the distance between the substrate and the ECR source be within 10 times the mean free path of the gas molecules.

FIG. 5 is a side view of a different example of the film-forming furnace used in the present invention, in which a plurality of ECR sources arranged adjacently as shown in FIG. ECR of
The ECR sources 24 arranged in the circumferential direction of the furnace are shifted in position in the longitudinal direction so that the phases of the constant pressure waves standing in the resonator do not overlap with each other in the longitudinal direction. It is installed on the furnace wall. By doing so, it is possible to form a film over a large area with high uniformity with a simple structure. Note that 15 is a drive/exhaust system.

FIG. 6 is a sectional view of still another example of the film forming furnace used in the present invention, in which the elongated rectangular parallelepiped ECR source shown in FIG. A plurality of resonators 25 each having an elongated rectangular parallelepiped resonance chamber are arranged in a plurality of rows in parallel to the axis and circumferentially, and a plurality of shafts 12 are arranged inside the resonators 25 so as to be able to rotate and revolve as shown by arrows. ing. Also with this film forming furnace, as in the example shown in FIG. 5, it is possible to form a film over a large area with high uniformity with a simple structure.

In the above example, SiH was used as the raw material gas.
Although we have explained the production of -3t film, aSi+-x C
X (1() (0<X≦1), a-3i+-y
L (H) (0<3F≦4/3), a-3i+-
Various amorphous silicon films such as wOx ()i) (0<y≦2), films containing polysilicon, a-3t-Z
nSe, a-ZnO1a-Ass Ses, a-S
The present invention is also effective for manufacturing films such as e/Te.

〔Effect of the invention〕

According to the present invention, an electron cyclotron resonance source having a rectangular parallelepiped resonance chamber is densely arranged around the substrate on which a film is to be formed, and the raw material gas is directly excited. It is possible to stably mass-produce photoreceptors with excellent properties.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an apparatus for carrying out the method of the present invention, FIGS. 2 and 3 are side views of examples of different arrangements of electron cyclotron resonance sources used in the method of the present invention, and FIG. A cross-sectional view of an electron cyclotron resonance source used in the invention method,
5 and 6 are side views and sectional views, respectively, of further different examples of the arrangement of the electron cyclotron resonance source used in the method of the present invention, and FIG. 7 is a sectional view of an apparatus for carrying out the conventional method. . 11... Film forming container, 12... Shaft, 13°24.25... Resonator (electron cyclotron resonance source)
20... Atomic gas introduction tube, 22... Plasma chamber. Figure 1 Figure 2 Figure 3

Claims (1)

[Scope of Claims] 1) A method for manufacturing an electrophotographic photoreceptor in which a photosensitive layer is formed using electron cyclotron resonance plasma, characterized in that an electron cyclotron resonance source with a resonant chamber having a rectangular parallelepiped shape is used. A method for manufacturing a photographic photoreceptor. 2) In the manufacturing method described in claim 1, a base body is installed on a shaft that is arranged so as to be able to rotate around its axis in a film forming container, and a source gas is excited by an electron cyclotron resonance source that is arranged around this base body. 1. A method for producing an electrophotographic photoreceptor, the method comprising forming a film on a substrate. 3) A method for manufacturing an electrophotographic photoreceptor according to claim 1, characterized in that a plurality of electron cyclotron resonance sources are arranged horizontally in a plurality of rows. 4) The manufacturing method according to claim 1 or 2, characterized in that the electron cyclotron resonance source is arranged in an angular range of more than 30 degrees to the left and right from a vertical line passing through the center of the film forming furnace. A method for manufacturing an electrophotographic photoreceptor. 5) A method for manufacturing an electrophotographic photoreceptor according to claim 1, characterized in that the film forming gas pressure is 100 mTorr or less. 6) A method for manufacturing an electrophotographic photoreceptor according to claim 1, characterized in that a film-forming raw material gas is directly supplied to the plasma chamber.