JPS5938371A - Production of photoreceptor - Google Patents

Abstract

PURPOSE:To form efficiently a stable photosensitive layer on the surface of a conductive substrate in the stage of producing the photoreceptor by photochemical reaction, by supplying a gaseous medium toward the surface of the substrate while moving the substrate at a prescribed speed. CONSTITUTION:A substrate 5 is rotated at a prescribed speed in a reactor 2 and electricity is conducted to a sheathed heater 17 to maintain the prescribed temp. on the lateral circumferential part of the substrate 5. A reacting gas is ejected from the ejection port 8a of an introducing pipe 7a under irradiation of UV light from a light source 15 toward the substrate 5 in the reactor 2. On the other hand, a carrier gas is admitted into a bomb 14 in which mercury vapor is stored to carry the mercury. The gaseous medium thus produced is ejected from the ejection ports 8b of the 2nd introducing pipe 7b. The UV light is irradiated to the position where the reacting gas and the gaseous medium coexist to induce photochemical reaction and the activated silicon molecules deposit on the surface of the lateral circumferential part of the substrate 5. An amorphous silicon film, etc. are uniformly formed by this method.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a photoreceptor by a photochemical reaction, and in particular, by controlling the location where a photosensitive layer is formed by the photochemical reaction, it is possible to manufacture a photoreceptor more efficiently (a good photoreceptor can be manufactured). This paper proposes a method.

Conventionally, optical CVD (chemical vapor d)
A method for manufacturing thin film semiconductors using a method called a deposition method is well known. In this method, for example, silane gas (S iH4
), low-pressure mercury lamp (wavelength 237.5 nm)
) to deposit and form an amorphous silicon film on a substrate disposed within a chamber.

However, in the above method, not only does the amorphous silicon adhere to unnecessary parts such as the mercury lamp and the walls of the chamber during the photochemical reaction, but also the light from the mercury lamp is blocked by the amorphous silicon attached to the substrate. This has the disadvantage that the amorphous silicon film cannot be transmitted to the top and the rate of deposition of the amorphous silicon onto the substrate is reduced, resulting in a reduction in the manufacturing efficiency of the amorphous silicon film both in terms of materials and time.

The present invention has been made in view of the above points,
fi! is a photoreceptor that can efficiently form a photosensitive layer through photochemical reactions. 'The purpose is to provide a manufacturing method. The first invention of the present application is characterized in that a photosensitive layer is formed in a container containing a conductive support. A reactive gas containing i as a component and a mediating gas that promotes the photochemical reaction are introduced from the outside, and the surface of the pre-distribution box support is irradiated with light having a wavelength in a predetermined range to form the photosensitive layer. In the method for producing a photoreceptor, which comprises activating a component and adhering the substance to the surface of the tetraelectric support to form a photosensitive layer, the above-mentioned component is introduced while repeatedly transferring and stirring the conductive support at a predetermined speed. The point is that the mediating gas is supplied toward the surface of the conductive support. Further, the special feature of the second invention is that a reactive gas containing a substance constituting the photosensitive layer as a component and a mediating gas that promotes a photochemical reaction are introduced from the outside into the container containing the conductive support. , a photosensitive method in which the surface of the conductive support is irradiated with light having a wavelength in a predetermined range to activate the substance constituting the photosensitive layer, and the substance is adhered to the surface of the conductive support to form a photosensitive layer. In the method for producing a body, the medium gas is heated, introduced into the container, and supplied toward the surface of the conductive support while repeatedly moving the conductive support at a predetermined speed.

FIG. 1 is a schematic diagram illustrating the principle of producing an amorphous silicon film by the method of the present invention. A reactive support 1 is placed in a container (not shown) configured to allow the introduction of various gases, and hydrogen silicide, especially 5IT (containing 5it), is placed near the surface of the support 1 as a reactive gas. mercury (Hg) vapor is supplied to promote the photochemical reaction.

Then, the reactive gas near the surface of the support 1 is irradiated with ultraviolet light at a frequency ν. Then, Hg vapor is photoexcited as shown in equation (1) below.

Hg + hν →Hg*−−−− −−−−
(1) Hg*: Photoexcited water (atom) Next, this photoexcited Hg* and SiH4 in the reaction gas react as shown in the following formula (2), and the water near the surface of the support 1 Activated silicide molecules are generated.

However, ・sin, ・SiH, ・H: activated SiH3,5il (, H molecule or atom, that is, Hg*
By the reaction between and SiH4, ・SiH3゜・SiH,・
An activated chain consisting of activated molecules or atoms such as H is formed near the surface of the support 1.

Then, these activated molecules such as SiH3 or -8iH adhere to the surface of the support 1, and an amorphous silicon film is formed on the surface of the support 1. In this way, a photochemical reaction occurs between the StH gas and the ultraviolet light using Hg vapor as a reaction promoting means, and an amorphous silicon film is formed on the surface of the support 1.

Next, specific embodiments of the first invention will be described based on the attached drawings. First, an embodiment of an apparatus for carrying out the method of manufacturing a photoreceptor of the present invention will be described. Second
FIG. 2(a) and FIG. 2(b) are a schematic plan view and a schematic front view showing an apparatus for manufacturing a photoreceptor according to the method of the present invention.

In order to vacuum the inside of the cylindrical quartz reactor 2, two pipes 3 and 3' extend from the right side of the figure and are connected to a rotary pump or the like (not shown) through the pulp 4 and 4'. ) is connected to the vacuum exhaust system. Inside this reactor 2, a cylindrical aluminum support 5 serving as a conductive support for the photoreceptor is placed in one dry part 2al of the reactor 2 so that the longitudinal axes of the supports 5 are parallel to each other. One end thereof is attached and set to a rotatably supported attachment shaft 6. The other end of the mounting shaft 6 that protrudes outward from the reactor 2 is connected to a driving means such as a motor (not shown), and therefore, the self-supporting body 5 is moved by this driving means. It is smoothly rotated once at a predetermined speed with nine centers around the longitudinal axis.

On the other hand, nose heaters 17 are evenly mounted on the inner surface of the side circumferential portion of the support body 5 over substantially the entire area thereof, and thermocouples 1
8 is introduced into the reactor 2, and its tip is brought into contact with the mounting shaft 6. These sheathed heaters 17 and thermocouples 18 are connected to a temperature control circuit 1 (H) disposed outside the reactor 2, and this temperature control circuit 19 is connected to #1.
．． The power supply to the sheathed heater 17 is controlled according to the surface temperature of the mounting shaft 6 detected by the couple 18, and the temperature of the side circumference of the support body 5, which has a certain correlation with the surface temperature of the mounting shaft 6, is controlled. The main feature is to maintain the optimum temperature for photochemical reactions.

Thus, a first introduction pipe 7a for introducing a reaction gas and a mixed gas, which will be described later, all at once, and a second introduction pipe 7a for introducing a medium gas for promoting a photochemical reaction, have their respective longitudinal axes aligned with the support 5.
They are arranged parallel to each other in the longitudinal axis direction and close to the side peripheral surface of the support body 5 to the same extent. Each inlet pipe 7a,
On the surface of 7b, multi-V gas ejection ports 8a and 8b are respectively formed at an appropriate distance apart from each other toward the surface g of the support 2. In this case, as shown in FIG. 2(a), the first introduction pipe 7a
The opening direction of the provided jet ports 8a and the second introduction pipe 7
It is desirable that the opening directions of the respective jet ports 8a and 8b are set so that they substantially intersect at the surface of the support 5. In this way, the spout ports 8a, 8
A more efficient photochemical reaction can be obtained by setting the opening direction of b and further setting the irradiation location of light in the photochemical reaction to the above-mentioned intersection location on the surface of the support 2.

The first of two. The second introduction pipes 7a, 7b pass through the end 2a of the reactor 2 and are externally connected to respective gas cylinders. That is, the first introduction pipe 7a passes through the pulp 9a externally and then connects to the two pipes 10a.

10′a, one pipe 10a is connected to the flow rate regulator 1
A cylinder 13 in which silane (SiH4) gas corresponding to a reaction gas is stored via 1a and pulp 12a, and a mixed gas including doping gas etc. is stored.
'a. Note that nitrogen gas was used as the doping gas in this example. On the other hand, the second introduction pipe 7b is
After passing through the pulp 9b externally, it is connected to a cylinder 14 for storing water vapor, and further, through this cylinder 14, through a pipe 10b, argon 'J4? The cylinder 13b is connected to the cylinder 13b.

The ultraviolet ray ″I+f：
A light source 15 is provided which irradiates the support body 5 within the reactor 2 with light. Note that the arrangement position of the light source 15 is, of course, not limited to the above-mentioned position. The light source 15 has a rod shape and is arranged parallel to the longitudinal axis of the reactor 2, and uses, for example, a 500 W low-pressure water lamp that emits ultraviolet light with a main wavelength of 253.7 nm. The light rays are uniformly irradiated over substantially the entire width of the side circumferential surface of the entire band-shaped support 2 along its longitudinal direction. Further, a reflection fi 16 is disposed on the back side of the light source 15 opposite to the side facing the reactor 2, and the light emitted from the light source 15 to this back side is also reflected by the reflecting mirror 16 and reacts. The structure is such that the light can be introduced into the vessel 2 and used effectively. In this case, in order to efficiently promote the photochemical reaction, two gas introduction pipes 7a, 7 are provided as described above.
It is desirable to set the arrangement of the light source 15 and the reflective brocade 16 so that the light irradiation location substantially coincides with the position on the surface of the support body 5 where the opening directions of the jet ports 8a and 8b intersect.

A process for manufacturing a photoreceptor using a photoreceptor manufacturing apparatus configured in a diagonal manner will be described in detail below. First, drive a rotary pump (not shown) as vacuum evacuation equipment,
The inside of the reactor 2 is brought into a vacuum state of, for example, about 10"5 Torr. Next, a motor (not shown) connected to the mounting shaft 61 is driven to rotate the support 5 at a predetermined speed, and the sheathed heater 17 is rotated. Start energizing.Then, it heats up.
The temperature control circuit 19 controls the energization according to the surface temperature of the mounting shaft 6 detected by the pair 18, and maintains the temperature of the side local portion of the support body 5 at, for example, about 200°C.

Next, a light source 15 is placed inside the reactor 2 in the above state.
For example, ultraviolet light with a wavelength of 253.7 nm is applied to the support 5.
While irradiating the side surface of the three cylinders 13a,
, 13'a, 13b are opened, and argon gas containing silane gas, doping gas, and daffodil vapor in the respective stored gases is jetted from the two inlet pipes 7a, 7b in the reactor 2 toward the surface of the rotating support 5. . That is, nitrogen gas as a mixed gas containing silane gas as a reaction gas and doping gas is passed from cylinders 13a and 13'a to pipe 1, respectively.
0a.

At 10'a, the pulps 12a and 12'a are individually adjusted to a predetermined flow rate by the flow rate regulator 11a and Il'al and flowed smoothly, and then they are combined and mixed, and the pulp 9a is bonded again. The water is ejected toward the surface of the support 5 from the ejection port 8a of the first introduction pipe 7a. On the other hand, argon gas as a carrier gas is supplied from the cylinder 13b to the pipe 10b.
From there, the water lobster is adjusted to a predetermined flow rate by the flow rate regulator 11b through the pulp 12b, and flows into the cylinder 141 in which the water lobster is stored, where the water lobster is softened and becomes a mediating gas that promotes photochemical reactions. , the pulp 9b is ejected from the ejection port 8b of the second introduction pipe 7b in a predetermined direction, and the first
The support body 5 rotates with the gas ejected from the introduction pipe 7a.
They collide and mix near the surface.

Then, in the position where this reaction gas and mediate gas etc. are mixed,
When the above-mentioned ultraviolet light is irradiated, the photochemical reactions represented by the above-mentioned formulas (1) and (2) occur, and the activated silicon molecules, 72+1-SjH, 5iH5, etc., form on the side peripheral surface of the support 5. Attach to. Since the support 5 is rotating at a predetermined rotational speed during the adhesion period of the silicon molecules, the silicon molecules, which are the products of the photochemical reaction, are located at a limited position on the support surface, that is, the photochemical reaction described above. Even if the amorphous silicon film is deposited only from the position 16 where C is generated, an amorphous silicon film is uniformly formed on the side peripheral surface of the support 5. In addition, since the raw material gas ejection position and the light irradiation position are approximately aligned to identify the zone where silicon molecules can be generated, they do not adhere to unnecessary locations in the reactor 2 as in the conventional technology, resulting in efficient and stable production. A desired amorphous silicon film can be formed.

In this example, the daffodil lamp of the light source 15 is installed outside the reactor 2, but it may be installed at an appropriate position inside the reactor 2. In this case, in order to identify the zone where a photochemical reaction occurs and the product adheres, the method of the present invention inadvertently attaches the product to the surface of the mercury lamp and the irradiated light traces the photochemical reaction. This eliminates the inconvenience of slowing down. Alternatively, the above-mentioned various gases may be collectively introduced into one introduction pipe and ejected from the surface of the support.

Here, a trial production test of a photoreceptor using the method of the present invention, which was carried out by the inventors of the present invention in order to confirm the effects of the method of the present invention, will be explained. The conditions set for the trial production are as follows.

Support specifications: 4 drums with an aluminum body of 80 mm outer diameter and 300 mm length. 500 W low-pressure mercury lamp (main wavelength 253.7 nm).
) Reaction gas: SiH4 gas, flow rate 20mt/9 mixed gas:
Nisso gas, flow i 30 ml/';) Carrier gas:
Argon gas, flow z 150 mt, i min. Number of rotations of the support: 10 r, p, m.

Heating temperature of support: 170°C Gas pressure inside the reactor: 2 torr Under these conditions, an amorphous silicon film with a thickness of 15 μm was formed.
As a result of the formation, the deposition rate of the amorphous silicon film was as fast as about 3 μm/hour. Further, the adhesion of the amorphous silicon film to unnecessary parts such as the side walls inside the reactor was negligible. Furthermore, the film quality of the amorphous silicon film produced in this test was extremely good as a photosensitive layer of a photoreceptor used in electrophotography. Further, the above manufacturing operation was repeated, and the photoreceptor could be manufactured with extremely high reproducibility and high stability. Moreover, since the photochemical reaction was generally mild, the surface of the support was not damaged.

Next, a specific example of the second invention of the present application will be described below. An apparatus for carrying out the method for manufacturing a photoreceptor according to the second invention is shown in Figure 3(a).

The schematic number of FIG. 3(b) is shown. The configuration of this device is almost the same as that of the device implementing the first invention, and the same reference numerals are given to the same components, and the description thereof will be omitted. The difference is that, as shown in Figure 3(a), in the route for delivering the mediating gas that promotes the photochemical reaction,
Sheathed heaters 2o are installed approximately evenly on the surface of the pipe from the cylinder 14 that stores mercury vapor to the 24th inlet pipe 7b, and a heat pair 21 that detects the surface temperature of this part;
A temperature control device flf 22 is provided which connects this thermocouple 21 to the sheathed heater 20, respectively, and controls the energization to the sheathed heater 20 according to the surface temperature detected by the thermocouple 21. The main point is that the system is configured to control the mercury vapor and heat the medium gas supply pipe containing mercury vapor to a predetermined temperature.

When a photoreceptor is manufactured using the above-described structure, the temperature of the medium gas is appropriately controlled, so that it is possible to more optimally control the amount of mercury used in the chemical reaction.

That is, by not only controlling the mercury vapor supply meter by adjusting the flow rate of argon gas, but also controlling the temperature of mercury vapor, which is easily liquefied, the amount of mercury supplied can be controlled more precisely. Therefore, in addition to the useful effects obtained by the method of the first invention, it becomes easier to optimize the photochemical reaction, and it becomes possible to more efficiently, stably, and produce high-quality photoreceptors.

Here, the test results of a photoreceptor produced as a prototype using the manufacturing method of the second invention described above will be explained. The conditions set for the trial production were the same as those for the test according to the method of the first invention, except that the mercury temperature was controlled at 40°C.

Under these conditions, an amorphous silicon film with a thickness of 15 μm was formed.
As a result, the deposition rate of the amorphous silicon film was faster at approximately 6 μm/hour.

In addition, good results similar to those obtained by the first method of the invention were obtained with respect to the location and condition of adhesion of the amorphous silicon film, its reproducibility, and its film quality.

As detailed above, according to the present invention, by controlling the location where the photochemical reaction occurs, the photosensitive layer as a product of the photochemical reaction can be efficiently and stably produced with good electrostatic quality in a short time. It becomes possible to form. Furthermore, by supplying the mediating gas that promotes the photochemical reaction under precise temperature control, it is possible to form a high-quality photosensitive layer more efficiently, rapidly, and stably. It should be noted that the present invention is not limited to the above-mentioned specific examples (it goes without saying that various modifications can be made within the technical scope of the present invention. It may be ejected from three or more directions so as to merge at one point.Alternatively, if the support is a flat plate, it may be moved back and forth in a straight line, etc., so that the photosensitive layer is uniformly formed on the surface of the support. The structure may be such that the support is repeatedly moved appropriately depending on the shape.

[Brief explanation of drawings]

Phase 1 diagram shows the principle of the photochemical reaction that is the basis of the method of the present invention, and Figures 2 (a) and 2 (b) are photosensitive diagrams showing a specific example of the first invention. FIG. 3A is a schematic plan view and a schematic front view of the body manufacturing apparatus; FIG. FIG. 3(b) is a schematic plan view and a schematic front view of a photoreceptor manufacturing apparatus showing a specific embodiment of the second invention. (Explanation of symbols) 1, 5: Support 2: Reactor 7a: First introduction pipe 7b: Second introduction pipe 8a, 8b:
Spout 14: Mercury pombe 15: Light source
17.20: Sheathed heater patent applicant Rico Co., Ltd. - Figure 1 hν

Claims (1)

[Scope of Claims] 1. A mediating gas that promotes a photochemical reaction of a reactive gas containing a substance constituting a photosensitive layer as a component is introduced from the outside into a container containing a conductive support, and the conductive support is The surface of the photosensitive layer is irradiated with 9 rays having a wavelength in a predetermined range to form a photosensitive layer of 41
A method for manufacturing a photoreceptor, which comprises activating the components of the substance that forms the substance and depositing the substance on the surface of the conductive support to form a photosensitive layer (in this method, the conductive support is moved at a predetermined speed). A method for producing a photoreceptor, characterized in that the medium gas introduced into the reactor gas is supplied toward the surface of the conductive support. 2. In the above item 1, the reaction gas contains hydrogen silicide. A method for producing a photoreceptor, characterized in that the medium gas contains mercury, and at least a portion of the photosensitive layer is amorphous silicon. 3. The photosensitive layer is formed in a container containing a conductive support. A reaction gas containing the substance as a component and a mediating gas that promotes a photochemical reaction are introduced from the outside, and the surface of the conductive support is irradiated with light having a wavelength in a predetermined region to activate the substance constituting the photosensitive layer. In the above-described manufacturing method in which the material is attached to the surface of the conductive support to form a photosensitive layer, the conductive support is moved at a predetermined speed while the medium gas is A method for producing a photoreceptor, characterized in that the photoreceptor is heated to a certain temperature, introduced into the container, and supplied toward the surface of the conductive support. A method for producing a photoreceptor, wherein the gas contains hydrogen silicide, the medium gas contains mercury, and at least a portion of the photosensitive layer is amorphous silicon.