JPS62172370A - Electrostatic copying machine - Google Patents

Abstract

PURPOSE:To prevent the curling of transfer paper by providing a metallic squeegee in tight contact with a photosensitive body formed by an electron cyclotron resonance CVD method or the combination use of said method and glow discharge CVD method. CONSTITUTION:A non-product gas (argon, etc.) is supplied into a resonance space and a magnetic field is applied thereto by an air core coil; at the same time, a microwave is supplied to the resonance space to excite the argon and to release the same into a reaction space. A product gas (monosilane, etc.) is released to the reaction space to excite and activate the monosilane by argon so that the film is formed on a base body drum by the cyclotron resonance CVD method to obtain a photosensitive drum 30. The photosensitive drum 30 may be formed by making combination use of the above-mentioned method and the glow discharge CVD method. The metallic squeegee 32 is provided in tight contact with the photosensitive body 30 to prevent the curling of the transfer paper 31. The generation of the peeling and exfoliation of the coating is eliminated by forming the photosensitive body 30 by the cyclotron resonance CVD method, etc., and therefore, the curling of the transfer paper is prevented by providing the squeegee in tight contact with said body.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application of the Invention The present invention provides a method of growing a film over a large area, particularly over a large area, by simultaneously using electron cyclotron resonance and a high frequency or direct current electric field. The present invention relates to an electrostatic copying machine that uses a vapor phase reaction (CVD) method to form a film on a surface to be formed, and is provided with a squeegee in close contact with a photoreceptor to prevent transfer paper from getting caught.

rPrior Art J Conventionally, a plasma CVD method (glow discharge CVD method) in which a reactive gas is activated by a high frequency or a direct current electric field has been used as a thin film forming technology using a gas phase reaction when manufacturing photoreceptors for electrostatic copying machines. Are known.

This method is superior to the conventional thermal CVD method in that it allows film formation at low temperatures. Furthermore, when the film to be formed is an amorphous silicon semiconductor or the like, it is possible to simultaneously contain hydrogen or a halogen element for neutralizing recombination centers, thereby making it possible to form a good PIN, PI, and Nl junction.

However, in this glow discharge CVD method, the film formation rate is extremely slow, and in practice, the growth rate is 10 to 10%.
It was required to be multiplied by 500 times.

Furthermore, when the film formed by this method has a thickness of about 1 μm at most, it peels off from the substrate or cracks due to changes over time or temperature changes. For this reason, it has been extremely difficult to provide a squeegee in close contact with the photoreceptor drum to prevent the transfer paper from getting caught.

In order to solve these problems, the present invention uses cyclotron resonance to activate a reactive gas, prepares a copying photoreceptor, and provides a squeegee in close contact with the photoreceptor. .

"Operation" For example, when trying to form an amorphous silicon semiconductor using only the direct excitation type glow discharge plasma CVD method,
Its growth rate is only 1 person/second. However, when the cyclotron resonance of the present invention is used alone or in combination, it is expected that this speed will be increased to 20 to 100 persons/second.

In the present invention, the power source for glow discharge is 13.5
A 6 MHz high frequency power source was used. However, even with DC glow discharge, the excited state of the excited reactive gas can be maintained.

Furthermore, cyclotron resonance uses an inert gas or a non-product gas (a gas that itself produces only a gas when decomposed or reacted). Argon is a typical inert gas. However, helium, neon, or krypton may also be used.

As non-product gases, in the case of oxide gases, oxygen, nitrogen oxides (NzO, NO, No□), carbon oxides (CO, C07
), water (+120) or nitrogen (NZ) as a nitride gas
, ammonia (NH3), hydrazine (N2H4), fluorocarbon (Nh, N2FJ), or a mixture thereof with a carrier gas or hydrogen.

In addition, as a reactive gas, as a product gas (a gas that decomposes or reacts to form a solid), silicide gas is 5i
nH2n-z (n≧1), 5tFn (n≧2), 5
iHnF4-, (1≦n≦4), germanium compound is GeHs + GeF4. .

GeHnF4-n (n=1+2,3), aluminum compound is 81 (C'ri) 3. AI (CzHs) i, A
lCl3. Gallium compound is Ga(CH+)i.

Ga (Cz's) ff, 5nC141Sn (C
H3) a + InCl31 In (CHi) 3
1SbC1:+, 5b(CH3)3 is a typical example. Furthermore, other product gases Bi2. It is also effective to add a doping gas such as BP+, PH3, AsH,3, etc. These non-product gases are activated by cyclotron resonance,
It mixes with the product gas in the reaction space outside this resonance region and transfers excitation energy to the product gas. Then, the product gas receives an extremely large amount of electromagnetic energy, so that the product gas can be activated by approximately 100x, and the product gas itself can retain that energy as activation energy, which is an internal pressure, rather than kinetic energy.

Alternatively, a glow discharge may be induced in the reaction chamber, and the excited or reactive product gas may be spread throughout the reaction chamber.

Further, by heating the substrate at a temperature of room temperature to 500°C, a film can be formed on the surface of the substrate to be formed.

The present invention will be illustrated below with reference to Examples.

Example 1 This example shows the production of a photoreceptor using a cyclotron resonance plasma CVD method.

FIG. 1 shows an outline of the apparatus used in this example.

In the drawing, a stainless steel container (1') has a lid (1'') and defines a reaction space (1).
In ゛), the base body (10) is provided inside the base body holder (10'), and the back side of the base body (10) is provided inside the base body holder (10'). A halogen lamp heater (7) is installed on the (1”) side, and when mounting the substrate, open i (1°°) upwards. Infrared rays are irradiated onto the substrate through the quartz window (19) to heat it. Furthermore, one mesh electrode (20°) is provided inside this substrate, and the other mesh electrode (20) is provided at the bottom of the container (1°), and a high frequency or DC current [(6) A high frequency electric field of 13.56 MHz or DC is applied to the substrate (10) perpendicularly to this electric field.
In the figure, it is located. However, a large number of substrates may be arranged vertically in parallel to the electric field. Furthermore, the base body is rotating in its circumferential direction.

In addition, the non-product gas is transferred from the doping system (13) to (18
) to the resonance space (2) made of a quartz tube (29). This resonant space has an air-core coil (5) outside it.

(5゛) and apply a magnetic field. At the same time, the microwave oscillator (3) passes through the analyzer (4), e.g.
GHz microwave is supplied to the resonant space (2).

In this space, if the non-product gas is argon in order to cause resonance, a magnetic field (for example, 875 Gauss) determined by its mass and frequency is applied by an air-core coil.

For this reason, the argon gas is excited and resonates at the same time as it is binned by the magnetic field, and after being sufficiently excited, the reaction space (1
) is released as electrons and excited argon gas (21
) to be done. At the outlet of this space, the product gas passes through a doping system (13) and a system (16), and then passes through a plurality of ring-shaped nozzles (
17) is released (22). As a result, the product gas (22) is excited and activated by the non-product gas (21). Additionally a pair of electrodes (20).

An electric field generated by (20') is simultaneously applied to these reactive gases.

As a result, even if the formation surface is sufficiently far from the resonance space (2) (generally 5 to 20 cm), the excited state of the reactive gas can be maintained.

In addition, in order to spread the reactive gas sufficiently in the reaction chamber and to activate the cyclotron, the pressure in the reaction space (1) and resonance space (2) is set to 1 to 10-' torr, for example, 0.03 to 0.0.
It was set to 01 torr. This pressure was achieved by adjusting the displacement of the vacuum pump (9) using a turbo pump together with the control valve (14) of the exhaust system (11).

Furthermore, in the drawing, one electrode (20) can also have the effect of a homogenizer (20) in order to sufficiently fill the reaction space with electron- or resonance-excited argon.

Then, the gas (21
) and the gas (22) from the nozzle (17) can be mixed over a wide area corresponding to the substrate surface, which is preferable because uniformity over a large area can be better obtained.

Of course, when such a homogenizer is used, collisions of electrons and active gas with this surface are unavoidable, resulting in energy consumption and a decrease in the growth rate. Therefore, if a higher growth rate is to be obtained, a lack of uniformity is observed, but this homogenizer effect can be removed and a mesh electrode with large openings simply provided. Unnecessary gas was exhausted through the exhaust system (11) from the exhaust port (8) in the peripheral area.

Experimental Example 1 In this experimental example, an amorphous silicon film was formed as the coating.

That is, the pressure in the reaction space was 0.003 torr, and argon was supplied from (18) at 20 SCCM as a non-product gas. In addition, monosilane was fed from (16) at IO5CCM.

Microwaves have a frequency of 2.45 GHz and 30-5
I adjusted the output of 00ga, for example, 50. Magnetic field (5), (
5'') resonance intensity was 875 Gauss.

A cylindrical substrate having at least a portion of an electrically conductive surface (
10), a non-single-crystal semiconductor, such as an amorphous silicon semiconductor, was formed on the surface to be formed, and unnecessary gas was discharged from the exhaust system (11). Then the board temperature is 250°C
A film formation rate of 45 people/second could be achieved in this method, and the film formation time was about 18 minutes. This speed is 30 times faster than the 1.5 person seconds obtained with plasma CVD alone.

The electrical properties of this amorphous silicon film include dark conductivity 2xlQ-10 (Scm-1) and optical conductivity (AMI
(under the condition of 100 mW/cm2) 7 X 10-'
(Scm-') could be obtained. This value is a characteristic similar to that of an amorphous silicon film in the hitherto known plasma CVD method, and the same high conversion efficiency can be obtained as a photoelectric conversion device having a PIN junction.

Furthermore, a 1 μm semiconductor film was formed. The film contains 0.1~
Plasma CVD with many pinholes with a size of 0.01μ
However, in the cyclotron resonance plasma CVD apparatus of the present invention, the number of pinholes is approximately 17.
10 (on average 1-3 games/field in the dark field of X100). 20th, the conductivity characteristics of this film after light irradiation are shown.

Despite the thickness of approximately 1 μm, light irradiation (AMllo
omW /ant) After 4 hours, almost no photodeterioration is observed, unlike the coating produced by the conventional method.

If the product gas is disilane or a mixed gas of monosilane and fluorinated silane (SizFa) instead of monosilane, further improvement in the film growth rate can be expected.

Next, a photosensitive drum for a copying machine was manufactured using this apparatus.

The substrate (10) was 25 cm in diameter and 30 cm in length, and its surface was covered with aluminum or a compound thereof. This substrate (10) is set in the apparatus shown in Fig. 1, and the pressure in the reaction space is 3 x 10-'! Tor
rAr20SCCM from (18)
CM, Bzl160.2SCCM was introduced from (16). After this, microwave output (2,45Gl+□) 50
W magnetic field strength 875 Gauss, plasma discharge type tA (13
, 56MH) at an output of 30 W, 500 to 2,000 people (700 people in this example) were formed semi-exclusively of P-type non-single crystal silicon.

After this, the reaction chamber was once evacuated and residual gas was exhausted to the outside of the reaction chamber.

Next, Ar25S was used to form an I-type non-single crystal silicon semiconductor.
CCM, Sit1415SCCM, a ■-type silicon semiconductor layer is placed on the P-type semiconductor layer with a thickness of 2 to 10 μm, in this example, about 5 μm.
m was formed. Other conditions were the same as in the case of the P-type semiconductor layer.

Next, 5i3Na-x was applied as a protective film on the I-type semiconductor layer.
In order to form (0≦x<4), 505 CCM of ammonia was introduced in addition to the conditions for forming an I-type semiconductor. This protective film was formed by several hundred people, in this example 200 people, and the photoreceptor of the copying machine was completed. The time it took to complete this entire process was approximately 30 minutes.

Example 2 A photoreceptor similar to that in Example 1 was produced using only cyclotron resonance. The manufacturing conditions were the same as in Example 1 +i.

However, in the case of only cyclotron resonance, there were some problems in forming a film over a large area, so in this example, the film was formed while rotating the substrate (10) and not moving it from side to side. Table 1 shows the results of 100 temperature cycles from room temperature to 15,000 degrees Celsius for the photoconductor produced according to this example. In this way, the film does not crack, peel off from the substrate, or bead, and the yield is approximately 9.
It was 8%.

Table 1 Also, install this Sample in an electrostatic copying machine and place it in close contact with this photoreceptor drum to prevent the transfer paper from getting caught.
Although a squeegee was provided, the semiconductor coating on the photoreceptor did not peel off from the substrate and remained unchanged even after 104 to 106 copying operations.

"Effects" The present invention uses only cyclotron resonance and a combination of cyclotron resonance and glow discharge to form a thick film very quickly when forming a photoreceptor for a copying machine. Further, as a characteristic of the film, the degree of photodeterioration of the I-type semiconductor layer is significantly lower than that of an amorphous silicon semiconductor formed by a general method. Therefore, it has excellent long-term reliability.

Furthermore, even when the film was about 10 μm thick, peeling, cracking, etc. did not occur, and the yield of the device was improved.

Therefore, the transfer machine (31) is placed in close contact with the photoreceptor drum (10).
) can be provided with a squeegee (32) to prevent it from getting caught. Furthermore, even with this squeegee (32) provided, the semiconductor layer did not come off from the base (10).

It goes without saying that the invention is not limited only to the examples. Furthermore, even if the P-type non-single-crystal silicon semiconductor is formed by the conventional glow discharge method in Example 1.2, the effects of the present invention will not change in any way.

[Brief explanation of drawings]

FIG. 3 shows the apparatus of the invention. (30)-1.--Photosensitive drum (31)...-11--Transfer paper (32)・−・・・Squeegee

Claims (1)

[Claims] 1. All or part of the coating forming the photoreceptor in a copying machine is coated with electron cyclotron resonance C.
In an electrostatic copying machine using a photoreceptor formed by the VD method alone or by a combination of electron cyclotron resonance and glow discharge CVD methods, a squeegee made of metal or a comparable material is provided in close proximity to the photoreceptor. An electrostatic copying machine characterized by: