JPH0627331B2 - Deposited film forming equipment - Google Patents

Description

The present invention relates to a functional film, in particular, an electronic device such as a semiconductor device, a photosensitive device for electrophotography, an optical input sensor device for an optical image input device, and the like. The present invention relates to a mass-production type film forming apparatus for semiconductor deposited films which is useful for applications.

[Conventional technology]

A plasma CVD (Chemical Vapor Deposition) method has been put into practical use as a film forming method for a photosensitive device for electrophotography.

In this method, the reaction chamber is depressurized to a high vacuum, the source gas is supplied to the reaction chamber, and then the source gas is decomposed by glow discharge to form a thin film on the substrate placed in the reaction chamber.

The amorphous silicon film prepared by using silane gas such as SiH ₄ Si ₂ H ₆ as a raw material gas by this method has relatively few localized levels existing in the forbidden band of amorphous silicon, and by doping with substitutional impurities The film forming method is capable of controlling valence electrons and has excellent characteristics as an electrophotographic photosensitive member.

FIG. 6 shows a basic structure of a main part of a preferred embodiment of a mass production type vacuum film forming apparatus of a conventional plasma CVD method. In accordance with this, film forming processing is performed on the surface of a cylindrical support. A case will be described in detail.

Reference numeral 611 denotes an intake chamber (base installation stage) for installing the cylindrical support 641 at a predetermined position, and by opening the door 615, one or a plurality of the cylindrical supports 641 are fixed to the fixing jig 61.
It is fixed at 6.

The intake chamber 611 is closed by closing the door 615 and using the exhaust system 631.
The inside pressure is reduced to a desired pressure and the support heater 624 is used to remove the cylindrical support 641 from, for example, 200 to 30.
Heat to about 0 ° C. After the temperature is sufficiently stabilized, the intermediate gate valve 6 is transferred to the relay chamber (relay stage) 612 which is kept at a desired vacuum pressure by the exhaust system 642 by the transfer means 617.
Open 19 and move the cylindrical support 641. After the movement, the gate valves 619 are closed, the gate valves 629 provided in the same number as the cylindrical support 614 are opened, and the vertical moving means 61 is moved.
8, the cylindrical support 641 is lowered, and a plurality of reaction furnaces (deposition stages) are provided corresponding to the respective gate valves.
Cylindrical support 64 in each of 614-1 and 614-2
Move each one.

After fixing each of the cylindrical support members 641 of the cylindrical support member receiving jig 627 rotatable by the drive source 637, the vertical movement means 618 returns to its original position.

After closing each of the gates 629, the reactors 614-1 and 6
14-2 by the exhaust system 632 and the introduction system 634 of the raw material gas for forming a film such as silane.
-2, the internal pressure is appropriately adjusted as desired, and then a high-frequency power source 633 applies a high-frequency voltage to the support and the coaxial cylindrical electrode 626 to cause discharge in the reaction furnaces 614-1 and 614-2. . By this discharge, the raw material gas such as silane introduced by the raw material gas introduction system 634 is decomposed to form an amorphous silicon film or the like on the surface of the cylindrical support 641. At that time, the cylindrical support 641 is heated from the inside by the heater 628 and rotated by the drive source 637 to make the film thickness uniform. The plasma generated by the discharge is generated by the electric shield 625 in the reaction furnaces 614-1 and 614-2.
Can be confined in a predetermined space.

After the film forming process is finished, the high-frequency power source is turned off at the same time the introduction of the raw material gas is stopped, and then the gate valve 629 is opened.
By the vertical movement means 618, each of the plurality of cylindrical support bodies 641 whose surfaces are formed into a film is pulled up to the relay chamber 612,
After that, the gate valve 629 is closed. Next, the gate valve 620 is opened, and each of the film-formed cylindrical supports 641 is moved to the take-out chamber (support take-out stage) 613, which has been depressurized to a predetermined pressure, by using the transfer means 621. After completion of the movement, the gate valve 620 is closed again. The cylindrical support 641 moved to the take-out chamber 613 is cooled by the cooling means 636 and is cooled by the cooling plate 623.
By the cooling action of, the temperature is lowered to a predetermined temperature under a predetermined reduced pressure. After that, the leak valve 639 is gradually opened so as not to adversely affect the formed film, and the leak chamber 639 is removed.
The inside of 13 is communicated with the outside air, and then the take-out door 622 is opened to take out the film-formed cylindrical support 641 to the outside.

By repeating the film forming operation process described above, film formation on a large number of substrates was continuously performed.

[Problems of conventional technology]

As described above, in the conventional plasma CVD method, it is necessary to introduce high-frequency power into the cylindrical substrate and the coaxial cylindrical utility pole in the reaction chamber in order to make the electrical properties and thickness of the deposited film uniform. It was

Therefore, it is difficult to simultaneously form a deposited film on one or more cylindrical substrates in one reaction chamber, and there is a problem in improving productivity.

Similarly, in the plasma CVD method, the cylindrical substrate and the coaxial cylindrical electrode are required in the reaction chamber, and the deposited film is deposited to the same thickness on both the cylindrical substrate and the coaxial cylindrical shape.
Only a small portion of the source gas was deposited on the desired cylindrical substrate. Therefore, the utilization efficiency of raw material gas is low,
There is a problem that the cost of the deposited film becomes high.

Further, in the plasma CVD method, since the source gas is decomposed and deposited by the high frequency energy introduced from the outside, it is difficult to efficiently introduce the high frequency energy into the reaction chamber, and the apparatus cost is increased.

〔Purpose〕

An object of the present invention is to eliminate the above-mentioned drawbacks of the deposited film forming apparatus and to provide an apparatus using a novel deposited film forming method that does not rely on the conventional forming method.

It is another object of the present invention to provide a deposited film forming method which can save energy, easily control the film quality, and obtain a deposited film having uniform characteristics over a large area.

Still another object of the present invention is to provide a deposited film forming method which is excellent in productivity and mass productivity, and which can easily obtain a film having high quality and excellent physical properties such as electrical, optical and semiconductor properties. is there.

[Outline of Invention]

The present invention excites by introducing a gaseous source material for forming a deposited film and a gaseous halogen-based oxidant having a property of oxidizing the source material into the reaction space and chemically contacting them. It is based on the finding that a precursor in a state is generated, and the precursor is used as a supply source of a deposited film forming element to form a deposited film on a substrate in a film formation space.

The deposited film forming apparatus of the present invention introduces a gaseous source material for forming a deposited film and a gaseous halogen-based acid agent having a property of oxidizing the source material into the deposited film forming chamber to form a chemical composition. For forming a deposited film by bringing them into contact with each other, a gas releasing means having a gas releasing pipe for releasing a gaseous raw material and a gas releasing pipe for releasing a halogen-based acid agent; A gas provided in a gas discharge pipe for discharging the gaseous raw material, comprising a support installation means for arranging a plurality of cylindrical supports for forming a deposited film around the discharge device, and the deposition film forming chamber. The discharge holes and the gas discharge holes provided in the gas discharge pipe for discharging the halogen-based acid agent are arranged so that the gases discharged from these gas discharge holes collide with each other.

The deposited film forming apparatus of the present invention is a deposited film forming apparatus system (cylindrical support charging and preheating device 401, shown in FIG.
Deposited film forming device 402, cooling device 403, unloading device 40
4 and a cylindrical support carrier device 405 to each device. ) Form a part of.

[Example embodiment]

FIG. 1 shows a sectional view of the deposited film forming apparatus of the present invention. In the deposited film forming apparatus of the present invention, in the central portion of the cylindrical deposited film forming chamber 100, there are 6 gas release pairs each including a deposited film forming gaseous source material release pipe 102 and a halogen-based oxidant release pipe 101. The installed gas releasing means, and the cylindrical support 105 around the gas releasing means, equidistant from the gas releasing means, to which the cylindrical support carrying jig 106 is attached so as to surround the gas releasing means. There is a cylindrical support installation jig (not shown) to be installed, and exhaust gas connected to an exhaust pump (not shown) for maintaining the deposition film formation chamber 100 at a predetermined internal pressure is provided on the inner wall of the deposition film formation chamber 100. It comprises a mouth 104 and a heater 103 for heating the cylindrical support 105.

FIG. 4 shows a schematic perspective view of the deposited film forming apparatus of the present invention.

A motor 30 for rotating the cylindrical support is provided outside the deposited film forming chamber.
1 and a motor controller 302, the motor 30
The power of 1 drives the cylindrical support rotating gears 304 and 303 in the deposited film forming chamber to rotate the cylindrical support at a predetermined rotation speed.

FIG. 2-1 (plan view) and FIG. 2-2 (elevation view) show schematic views of the gas discharge pipe in the deposited film forming apparatus of the present invention.

The deposited gas forming gaseous source material discharge pipe 202 and the halogen-based oxidant discharge pipe 201 are installed adjacent to each other. Each gas discharge pipe has a gas discharge hole 2 in the longitudinal direction of the gas discharge pipe.
03 can be opened. The gas emitted from the gas emission holes of each gas emission pipe is emitted in the direction in which the gases collide with each other, as indicated by 204.

By disposing the cylindrical support around the gas discharging means as described above, the discharged gaseous raw material for forming a deposited film can be effectively used. Further, by arranging the gas discharge pipe pair in a direction in which the gaseous raw material for forming a deposited film discharged from the gas discharge hole and the gaseous halogen-based oxidant collide with each other, the chemical reaction of the gas is promoted and the utilization efficiency is improved. Can be raised.

Further, in the present invention, the deposited film forming supports are arranged equidistantly around the gas releasing means, and each of them rotates on its own axis, so that the deposited film can be uniformly formed on a large number of supports.

Further, in the present invention, since the spontaneous chemical reaction between the raw material and the halogen-based oxidant is utilized, energy for promoting the reaction is unnecessary, and the deposited film forming apparatus has a simple structure, resulting in a cost reduction of the apparatus. Is cheaper, and it is easy to manage the device during mass production.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example An electrophotographic image forming member using an amorphous silicon (A-SilH) film was produced using the deposited film forming apparatus of the present invention schematically shown in FIGS. 1 to 4.

The layer structure of the electrophotographic image forming member at this time is shown in FIG.

That is, the electrophotographic image forming member shown in FIG. 5 includes a support (Al) 500, a charge injection blocking layer (P ⁺ type A) from the support.
-SilH) 501, a photosensitive layer (A-SilH) 502, and a surface protective layer (A-SiClH) 503.

The production process will be described in detail below.

Six Al-made cylindrical supports having a diameter of 80 mm were attached to a carrying tool and placed in a preheating device 401. The inside of the preheating device was set to about 10 ⁻³ Torr by an exhaust pump (not shown), and Ar gas was caused to flow into the preheating device 401 to set the internal pressure to 0.
It was set to 6 Torr. The preheating heater was turned on and the support temperature was set to 250 ° C. After the support temperature reached 250 ° C., introduction of Al gas into the preheating chamber was stopped and the inside of the preheating device was set to about 10 ⁻³ Torr. Then 1
Six cylindrical supports were transferred from the preheating device 401 to the deposited film forming device 402 exhausted to 10 ^-3 Torr by the cylindrical support transfer device exhausted to 0 ^-3 Torr. Six cylindrical supports were installed as shown in FIG. After that, the motor 301 shown in FIG. 3 was operated, and the motor 301 was set so that the support rotated once per minute. After the rotation of the support is stabilized, switch on the heater 103 shown in FIG.
The temperature of the heater 103 was set so that the support temperature could be kept at 250 ° C. After the temperature of the support is stabilized, first, a mixed gas (SiH ₄ : NO) of silane gas (SiH ₄ ), diborane gas (B ₂ H ₆ ) and nitric oxide gas (NO) gas is discharged from the gaseous raw material release pipe for forming a deposited film. : B ₂ H ₆ = 10: 3: 0.01)
2,000 SCCM was released, and F ₂ gas was released by 1,000 SCCM from the gaseous halogen-based oxidant release tube and reacted for 30 minutes to form a charge injection blocking layer of 3 μm on the Al support. Thereafter, SiH _4, B ₂ H _6, NO gas mixture of gas, are switched sequentially to the gas SiH ₄ (not shown switching Yotsute the device) and SiH ₄ gas was released from the raw material discharge pipe 180 minutes After the reaction, a photosensitive layer having a thickness of 18 μm was formed on the charge injection blocking layer. Then, the SiH ₄ gas was continuously changed to a mixed gas of SiH ₄ gas and CH ₄ gas (SiH ₄ : CH ₄ = 1: 10), and 1.00
Release 0 SCCM and react for 30 minutes, then on the photosensitive layer,
A 0.5 μm surface protective layer was formed.

After deposition of the electrophotographic image forming member, the emission of each gas was stopped
Purging is performed to bring the deposition apparatus to an internal pressure of 10 ⁻³ Torr, and the six support members are moved to the cooling device 403 by the transfer device 405, and after cooling, they are moved from the cooling device 403 to the unloading device 404 by the transfer device 405, and then unload The apparatus 404 was leaked to atmospheric pressure with Ar, and the electrophotographic image forming member was taken out.

The deposited electrophotographic imaging member has a uniform film thickness,
It showed sufficient properties for practical use as an electrophotographic image forming member. The utilization efficiency of the raw material gas exceeded 70%.

〔The invention's effect〕

(1) The cost of the device is low because a large number of films can be uniformly formed at one time with one deposition film forming device.

(2) Since the support is arranged around the gas discharge pipe, the gas utilization rate is high and the raw material cost of the deposited film is low.

(3) Since the gaseous raw material and the halogenated oxidant are efficiently mixed, the reaction efficiency is good and the gas utilization efficiency is high.

(4) In addition to heating the support, energy from the outside is unnecessary, so the running cost of the device is low.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a deposited film forming apparatus of the present invention, FIGS. 2-1 and 2-2 are schematic explanatory views of a gas discharge tube of the present invention, and FIG. 4 is a schematic perspective view of the deposited film forming apparatus of FIG. 4, FIG. 4 is an explanatory view of a deposited film forming apparatus system having the deposited film forming apparatus of the present invention as a constituent element, and FIG. 5 is an electron formed by an embodiment of the present invention. FIG. 6 is an explanatory view of a layer structure of a photographic image forming member, and FIG. 6 is a schematic explanatory view of a conventional plasma CVD mass-production type vacuum film forming apparatus. 100,309 ... Deposited film forming chamber, 101,201 ...
Halogen-based oxidant discharge pipe, 102, 202 ... Gaseous raw material discharge pipe, 103 ... Heater for heating support, 10
4, 308 ... Exhaust port, 105, 205, 305 ... Cylindrical support, 106, 306 ... Cylindrical support carrying jig, 201 ... Halogen-based oxidant discharge pipe, 202 ... Gaseous Raw material discharge pipe, 203 ... Gas discharge hole, 204 ...
... Gas release direction, 301 ... Cylindrical support rotation motor, 302 ... Motor controller, 303, 30
4 ... Cylindrical support driving gear, 307 ... Gaseous source material discharge pipe, halogen-based oxidant discharge pipe pair, 401 ... Preheating device, 402 ... Deposited film forming device, 403 ... Cooling device, 404 ... carry-out device, 405 ... carrier device, 5
00 ... Support, 501 ... Charge injection blocking layer, 502 ...
... Photosensitive layer, 503 ... Surface protective layer, 611 ... Substrate intake chamber, 612 ... Relay chamber, 613 ... Substrate removal chamber, 614 ... Reactor, 615, 22 ... Door, 616 ...
... Substrate fixing jigs, 617, 21 ... Transporting means, 618 ...
... Up / down moving means, 619, 20, 29 ... Gate valve,
623 ... Cooling plate, 624, 28 ... Heater, 6
30 ... Heater power source, 631, 32, 35, 42 ...
Exhaust system, 633 ... High frequency power source, 634 ... Raw material gas introduction system, 636 ... Cooler, 638, 39, 40 ... Leak valve, 641 ... Cylindrical support.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location H01L 31/04

Claims (3)

[Claims] 1. A gaseous source material for forming a deposited film and a gaseous halogen-based acid agent having a property of oxidizing the source material are introduced into a deposited film forming chamber and brought into chemical contact with each other. A deposited film forming apparatus for forming a deposited film by means of the above, comprising a gas releasing means having a gas releasing tube for releasing a gaseous raw material and a gas releasing tube for releasing a halogen-based acid agent, and the periphery of the gas releasing means. And a support installation means for arranging a plurality of cylindrical supports for forming the deposited film in the deposited film forming chamber, and a gas release hole provided in the gas release pipe for releasing the gaseous raw material and the support. A deposition film forming apparatus characterized in that a gas discharge hole provided in a gas discharge pipe for discharging a halogen-based acid agent is arranged in a direction in which gases discharged from these gas discharge holes collide with each other. 2. The gas discharge pipe of each of the claims, wherein at least two or more gas discharge holes are formed.
The deposited film forming apparatus according to item. 3. The cylindrical support installation means is circularly arranged around the gas discharge means.
The deposited film forming apparatus according to item.