JP2656020B2 - Deposition film forming equipment - Google Patents

Description

The present invention relates to a functional film, particularly to an electronic device such as a semiconductor device, a photosensitive device for electrophotography, and a light input sensor device for an optical image input device. The present invention relates to a semiconductor deposition film forming apparatus useful for applications.

[Conventional technology]

Heretofore, for a functional film, particularly a non-crystalline chamber or a polycrystalline semiconductor film, a film forming method which is individually suitable from the viewpoint of desired physical properties and applications has been adopted.

For example, if necessary, amorphous or polycrystalline non-single-crystal silicon (hereinafter referred to as “NON-Si ( H, X) "
Abbreviated as "a-Si (H, X)" when indicating amorphous silicon, and "poly-Si (H, X)" when indicating polycrystalline silicon.) Silicon-based deposited film such as a film (microcrystalline silicon is commonly called a-Si (H, X)
However, vacuum deposition, plasma CVD, thermal CVD, reactive sputtering, ion plating, photo-CVD, etc. have been attempted.

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

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

An amorphous silicon (a-Si) film formed by this method using a silane gas such as SiH ₄ or Si ₂ H ₆ as a raw material is an amorphous silicon (a-Si) film.
Has a relatively small number of localized levels in the forbidden band, and can control valence electrons by doping with substitutional impurities.
This is a film forming method capable of obtaining an electrophotographic photosensitive member having excellent characteristics.

FIG. 6 shows a basic configuration of a main part of a preferred embodiment of a conventional mass-production type vacuum film forming apparatus of the plasma CVD method, in which a film forming process is performed on the surface of a cylindrical substrate in accordance therewith. And will be described specifically.

Reference numeral 611 denotes an intake chamber (base setting stage) for setting the cylindrical base 641 at a predetermined position. The door 615 is opened, and one or a plurality of cylindrical bases 641 are fixed to the fixing jig 616.

The door 615 is closed, the inside of the intake chamber 611 is reduced to a desired pressure by the exhaust system 631, and the cylindrical heater 641 is heated to about 200 to 300 ° C. by the base heater 624. After the temperature is sufficiently stabilized, the intermediate gate valve 619 is opened by the transfer means 617 in the relay chamber (relay stage) 612 maintained at a desired vacuum pressure by the exhaust system 642, and the cylindrical base body is opened.
Move 641. After the movement, the gate valves 619 are closed, the gate valves 629 provided in the same number as the cylindrical substrates 641 are opened, and the cylindrical substrates 641 are lowered by the vertical movement means 618, and a plurality of reactors provided corresponding to each gate valve are provided. (Film Forming Stage) Each of the cylindrical substrates 641 is moved into each of 641-1 and 641-2.

Cylindrical substrate receiving jig 627 rotatable by drive source 637
After fixing each of the cylindrical base bodies 641 to the respective members, the vertical movement means 618 returns to the original position.

After closing each of the gates 629, the reactors 614-1 and 614-2 are closed.
The internal pressure of the reaction furnaces 614-1 and 614-2 is appropriately adjusted as desired by an exhaust system 632 and an introduction system 634 for a source gas for film formation such as silane. A high frequency voltage is applied to 626 to cause a discharge in the reactors 614-1 and 614-2. By this discharge, the source gas such as silane introduced in the source gas introduction system 634 is decomposed, and an amorphous silicon film or the like is formed on the surface of the cylindrical substrate 641. At that time, the cylindrical substrate 641 is heated from the inside by the heater 628 and is rotated by the drive source 637 to uniform the film thickness. The plasma generated by the discharge is trapped by the electric shield 625 in a predetermined space of the reactor 614-1, 614-2.

After the end of the film forming process, the introduction of the raw material gas is stopped, and at the same time, the high frequency power supply is turned off.
Each of the plurality of cylindrical substrates 641 having the surface formed thereon is lifted to the relay chamber 612 by the vertical movement means 618, and then the gate valve 629 is closed. Next, the gate valve 620 is opened, and each of the film-formed cylindrical substrates 641 is moved to the take-out chamber (support take-out stage) 613, which has been reduced to a predetermined pressure in advance, by using the transfer means 621. After the movement is completed, the gate valve 620 is closed again. The cylindrical substrate 641 moved to the take-out chamber 613 is cooled to a predetermined temperature under a predetermined reduced pressure by the cooling action of the cooling plate 623 cooled by the cooling means 636. Thereafter, the leak valve 639 is gradually opened so as not to have an adverse effect on the formed film, the inside of the take-out chamber 613 is communicated with the outside air, and then the take-out door 622 is raised, so that the formed cylindrical substrate 641 is exposed to the outside. To take out.

By repeatedly performing the above-described film forming operation process, film formation on a large number of substrates has been continuously performed.

[Problems of conventional technology]

As described above, in the conventional plasma CVD method, it is necessary to introduce high-frequency power to the cylindrical substrate and the coaxial cylindrical electrode in the reaction chamber in order to make the electrical properties and the film thickness of the deposited film uniform. 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, a cylindrical substrate and a coaxial cylindrical electrode are required in the reaction chamber, and the deposited film is deposited on both the cylindrical substrate and the coaxial cylindrical shape to a similar thickness.
Only a small portion of the source gas was deposited on the target cylindrical substrate. As a result, the utilization efficiency of the source gas is low,
There is a problem that the cost of the deposited film is increased.

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 there has been a problem that the apparatus cost is increased.

In addition, there are several problems in process operation and also in capital investment. Regarding the process operation, for example, take the parameters of the substrate temperature, the flow rate and flow ratio of the introduced gas, the pressure at the time of forming the layer, the high-frequency power, the electrode structure, the structure of the reaction vessel, the pumping speed, and the correlation among the plasma generation method. Many parameters already exist, and there are other parameters as well, and it is necessary to select strict parameters to obtain a desired product, and since these parameters are strictly selected, One of the factors, particularly plasma, which is unstable when it is in an unstable state, is significantly adversely affected and cannot be realized as a product. As for the device, since strict selection of parameters is required as described above, the structure is naturally complicated, and it is designed to respond to individually selected parameters if the device scale and type are changed. Must. For these reasons, plasma CVD
As for the method, although it is considered to be the most suitable method at present, from the above, if a desired a-Si film is to be mass-produced, a large capital investment is required for the apparatus. As described above, the process control items are many and complicated, the process control tolerance is narrow, and the equipment adjustment is delicate. There is.

On the other hand, photosensitive devices for electrophotography have been diversified, and the requirements for various characteristics and the like have been generally satisfied, and at the same time, the electrophotographic photosensitive device composed of a stable a-Si film corresponding to the application target and application has been developed. It is a social requirement that devices be constantly supplied at low cost, and there is a need for the development of methods and apparatuses that meet this requirement.

This also applies to other layers such as an a-Si film containing at least one selected from oxygen, carbon and nitrogen atoms.

Further, in the case of forming a semiconductor device having a multilayer structure, the interface between the respective layers is a factor that deteriorates the characteristics of the semiconductor device to be obtained. As shown, an anti-reflection layer (first layer, an amorphous silicon germanium layer whose band gap is controlled by Ge) 501 and a charge injection blocking layer (second layer) are formed on an Al base 500.
Layer, B-doped amorphous silicon layer) 502, photosensitive layer (third layer, undoped amorphous layer) 503,
A surface protection and light absorption enhancement layer (fourth layer, amorphous silicon carbide layer) 504 is deposited. Since the types and flow rates of the source gases for forming the respective deposited layers and the discharge intensity of the plasma are extremely different, the first layer and the second layer are usually used.
Between the layers, between the second and third layers, and between the third and fourth layers, the discharge is stopped to completely convert the gas,
Alternatively, efforts have been made to reduce the influence of the interface generated between the deposition layers by providing a variable layer in which the gas type, flow rate or plasma discharge intensity is gradually changed continuously. However, in any case, no satisfactory improvement in the change of the interface characteristics has been recognized.

As described above, there is still a point to be solved in the formation of a silicon-based deposited film, and its practical characteristics,
There is a strong need for the development of a deposited film forming apparatus that can be mass-produced by maintaining energy uniformity with a low-cost apparatus while maintaining uniformity, and to improve the interface state of a multilayered deposited film such as an electrophotographic photosensitive device. I have.

[Object of the invention]

An object of the present invention is to eliminate the above-described drawbacks of the deposited film forming apparatus and to continuously manufacture semiconductor devices such as electrophotographic photosensitive devices using a novel deposited film forming method which is not based on a conventional forming method. The present invention is to provide a device that can be used.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a multi-layer deposited film that is not limited to a plasma reaction and is capable of conserving energy while at the same time controlling film quality easily and improving interface characteristics with uniform characteristics over a large area. It is intended to provide a deposited film forming apparatus which can be formed on a substrate.

Still another object of the present invention is to provide a deposition film forming apparatus which is excellent in productivity, mass productivity, easily obtains a high-quality electrical, optical, and multi-layer deposited film having excellent physical properties such as semiconductor properties. It is also to provide.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a gaseous raw material for forming a deposited film and a gaseous oxidizing agent having a property of oxidizing the raw material are brought into contact with each other and deposited on a substrate. In the apparatus for forming a film, a gaseous source material discharge hole connected to the gaseous source material supply pipe at a position symmetrical with respect to the substrate on both opposed wall surfaces of a deposition film formation chamber, and the gaseous oxidizing agent A support for forming a deposited film, comprising: a mixing / discharging means alternately having gaseous oxidant discharging holes connected to a supply pipe; and a gas exhaust hole, and at least a part in a plane connecting the mixing and discharging means. The present invention has been completed by connecting a plurality of deposition film forming chambers provided with the installation means.

(Operation)

According to the above-described deposited film forming apparatus of the present invention, energy saving and large area can be achieved simultaneously without using a plasma reaction.
Multi-layer deposited film that satisfies film thickness uniformity and film quality uniformity and has improved interface characteristics simplifies management and mass-produces, and does not require large equipment investment in mass-production equipment In addition, the control items for mass production become clear, the control allowance is wide, and the adjustment of the apparatus can be easily performed continuously.

In the film forming film forming apparatus of the present invention, a gaseous raw material used for forming a deposited film and a component serving as a valence electron controlling agent and / or a component serving as a forbidden band width controlling agent are used as constituent elements. The substance (D) is oxidized by contact with a gaseous oxidizing agent, and the type of the target deposited film,
It is appropriately selected as desired depending on the characteristics, use, and the like. In the present invention, the gaseous raw material, the gaseous substance (D), and the gaseous oxidizing agent may be those that are introduced into the reaction space and made gaseous when they come into contact with each other. In the usual case, it may be gas, liquid or solid.

When the raw material, the substance (D) or the oxidizing agent for forming a deposited film is liquid or solid in a normal state, Ar, H
e, as N _2, using a Kiyari Argus of H _2, etc., raw materials for formation of the deposited film into the reaction space by performing bubbling with also adding heat as required, material (D) and oxidant gaseous Introduce.

At this time, the partial pressure and the mixing ratio of the gaseous raw material, the gaseous substance (D), and the gaseous oxidizing agent adjust the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous oxidizing agent. It is set by the following.

As a raw material for forming a deposited film used in the present invention, for example, a linear or branched chain silane compound may be used as long as a semiconductor or electrically insulating silicon deposited film is obtained. And a cyclic silane compound.

Specifically, as the linear silane compound, SinH _{2n + 2}
= (N = 1,2,3,4,5,6,7,8), SiH ₃ SiH (SiH ₃ ) SiH ₂ SiH ₃ as a branched chain silane compound, and SinH ₂ n as a cyclic silane compound (N = 3, 4, 5, 6).

Of course, these silicon-based compounds can be used alone or in combination of two or more.

The gaseous oxidizing agent used in the present invention is made gaseous when introduced into the reaction space, and is effective only by contacting the gaseous raw material for forming a deposited film which is simultaneously introduced into the reaction space. Oxidizing agents that have an oxidizing property, and include oxygen-based oxidizing agents, nitrogen-based oxidizing agents, and halogen-based oxidizing agents. Specifically, air, oxygen, oxygens such as ozone, N
_{2 O 4, N 2 O 3} , N2 2, oxygen or a compound of nitrogen such as NO, H ₂
Peroxides such as O ₂ and halogen gases such as F ₂ , Cl ₂ , Br ₂ , I ₂ and ClF can be mentioned as effective ones.

These oxidizing agents are in a gaseous state, are supplied with a desired flow rate and supply pressure together with the gas of the raw material for forming the deposited film and the gas of the substance (D), and are introduced into the reaction space to be supplied with the raw material. A chemical reaction is caused by mixing and collision with the substance and the substance (D), thereby oxidizing the raw material and the substance (D) to efficiently convert a plurality of kinds of precursors including a precursor in an excited state. Generate. The generated excited state precursors and other precursors serve as sources of the components of the deposited film on which at least one of them is formed.

The generated precursor decomposes or reacts to form a precursor in another excited state or a precursor in another excited state, or emits energy as necessary but forms a film as it is By touching the substrate surface arranged in the space,
When the substrate surface temperature is relatively low, a deposited film having a three-dimensional network structure is formed, and when the substrate surface temperature is high, a crystalline deposited film is formed.

In the present invention, the deposited film forming process proceeds smoothly, a film having high quality and desired physical characteristics can be formed, and the types and the types of the raw material and the halogen-based oxidizing agent as film forming factors The combination, the mixing ratio thereof, the pressure during mixing, the flow rate, the internal pressure of the film formation space, the gas flow type, and the film formation temperature (substrate temperature and ambient temperature) are appropriately selected as desired. These film formation factors are organically related and are not determined independently, but are determined according to each other in a mutual relationship.

In the present invention, the ratio of the introduction amount of the halogen-type oxidizing agent and the oxygen-based or / and nitrogen-based oxidizing agent into the reaction space is as follows:
It is appropriately determined according to the type of the deposited film to be formed and the desired properties, but is preferably 1000/1 to 1/50, more preferably 500/1 to 1/20, and most preferably 100/1 to 1 / 10 is desirable.

In the method of the present invention, the substance (D) containing a component serving as a valence electron controlling agent and / or a component serving as a forbidden band control agent as a constituent element is in a gaseous state at normal temperature and normal pressure, or at least is deposited. It is preferable to select a compound which is gaseous under film forming conditions and can be easily vaporized by an appropriate vaporizer.

As the substance (D) used in the present invention, in the case of a silicon-based semiconductor film, a p-type valence electron controlling agent, an element belonging to Group IIIA of the periodic table which acts as a so-called p-type impurity, for example, B , Al, Ga, In, Tl and the like, and an n-type valence electron controlling agent, an element of Periodic Table Group V A acting as a so-called n-type impurity, such as N, P, As, Sb, Bi, etc. Including compounds.

_{Specifically, NH 3, HN 3, N} 2 H 5 N 3, N 2 H 4, NH 4 N 3, PH 3, P 2 H 4, A
sH ₃ , SbH ₃ , BiH ₃ , B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆ H ₁₂ , Al
(CH ₃ ) ₃ , Al (C ₂ O ₅ ) ₃ , Ga (CH ₃ ) ₃ , In (CH ₃ ) _{3 and the} like can be mentioned as effective ones. These valence electron controlling agents can be used as a forbidden band width adjusting agent by adding in a large amount.

Examples of the compound containing a forbidden band width controlling agent, a so-called forbidden band width expanding element, include a carbon-containing compound, an oxygen-containing compound, and a nitrogen-containing compound.

Specifically, as the carbon-containing compound, for example, a chain or cyclic hydrocarbon compound and a compound in which part or all of the hydrogen atoms of the chain or cyclic hydrocarbon compound are substituted with halogen atoms are used. for example C _n H _{2n +} 2 _(n is an integer of 1 or more), CnH _{2n +} 1 (n is an integer of 1 or more), CnH _2n (n
Is a saturated and unsaturated hydrocarbon represented by 1 or more, or CuY ₂ u ₊₂ (u is an integer of 1 or more, and Y is at least one element selected from F, Cl, Br and I). ), A cyclic silicon halide represented by CvY ₂ v (v is an integer of 3 or more, and Y has the above-mentioned meaning), and CuHxYy (u and Y have the above-mentioned meanings).
x is a + y = ₂ u or ₂ u _+2. And the like.

These carbon compounds may be used alone or in combination of two or more.

O ₂ , CO ₂ , NO, NO ₂ , N ₂ O, O ₃ , CO, H ₂
Compounds such as O, CH ₃ OH, CH ₃ CH ₂ OH and the like can be mentioned.

Nitrogen-containing compounds include N ₂ , NH ₃ , N ₂ H ₅ N ₃ , N ₂ H ₄ , NH ₄ N ₃
And the like.

As the forbidden band width controlling agent used in the present invention, a compound containing a so-called forbidden band width reducing element, for example, a germanium compound, a tin compound and the like can be mentioned as effective ones.

Specifically, as the compound having germanium as a main skeleton, for example, a chain or cyclic germanium compound and a compound in which one to all hydrogen atoms of a chain or cyclic germanium compound are substituted with a halogen atom, Specifically, for example, Ge _S H _{2S + 2} (S = 1, 2, 3, 4, 5, 6), Ge _t
H _2t (t = 3,4,5,6), Ge _u Y _{2u + 2} (u is an integer of 1 or more, Y
Is at least one element selected from F, Cl, Br and I. ) Chain germanium halide GevY
₂ v (v is an integer of 3 or more, Y may have. The abovementioned meaning) cyclic germanium halide represented by (the u and Y is x + y = 2u or 2u + 2 have the abovementioned meaning.) Ge _u HxYy in Is shown. Examples thereof include a chain or cyclic compound. The tin compounds include hydrogen tin, such as, for example, SnH _4.

To introduce the gas of the substance (D) into the reaction space,
It can be introduced in advance by mixing with the raw material for forming the deposited film, or can be introduced from a plurality of independent gas supply sources.

In the present invention, the raw material and the substance (D) for forming a deposited film as a film forming factor can be formed so that the deposited film forming process smoothly proceeds and a film having high quality and desired physical characteristics is formed. And the type of oxidizing agent, and their mixing ratio,
The pressure during mixing, the flow rate, the internal pressure of the film forming space, and the film forming temperature (substrate temperature and ambient temperature) are appropriately selected as desired. These film formation factors are organically related and are not determined independently, but are determined according to each other in a mutual relationship.

In the present invention, the ratio of the amount of the gaseous raw material and the amount of the gaseous oxidizing agent to be introduced into the reaction space for forming a deposited film depends on the relationship between the above-mentioned film forming factors and the related film forming factors. It is appropriately determined as desired, but in the introduction flow rate ratio, preferably,
1/2 to 100/1 is appropriate, and more preferably 1/5 to 50/1.

The ratio of the introduced amount of the gaseous substance (D) is appropriately set as desired in accordance with the type of the gaseous raw material and the desired semiconductor characteristics of the deposited film to be formed. If so, the gaseous raw material, preferably 1/1000000 to 1/10, more preferably 1/100
It is desirable to be 000 to 1/20, optimally 1/100000 to 1/50.

If the purpose is to control the forbidden bandwidth, for the gaseous raw material, preferably, 1/10000 to 1000/1, more preferably 1/1000 to 500/1, optimally 1/100 to Desirably 100/1.

In order to stochastically increase the contact between the gaseous raw material and the gaseous substance (D) and the gaseous oxidizing agent, the pressure at the time of mixing when introduced into the reaction space is preferably higher. It is preferable to determine the optimum value as needed in consideration of reactivity. The pressure at the time of mixing is determined as described above, but the pressure at the time of each introduction is preferably 1 × 10 ⁻⁷ atm to 5 atm, more preferably 1 × 10 ⁻⁶ atm.
Desirably, the pressure is set to 2 atm.

The pressure in the film formation space, that is, the pressure in the space in which the gas to be formed on the surface is disposed, depends on the precursor (E) in the excited state generated in the reaction space and, in some cases, the precursor (E). The precursor (F) derived from the body (E) is appropriately set as desired so as to effectively contribute to the film forming process.

The pressure in the film formation space in the present invention is determined by the relationship between the gaseous raw material introduced into the reaction space, the gaseous substance (D), and the introduction pressure of the gaseous oxidizing agent. Torr to 100 Torr, more preferably 0.01 Torr to
It is desirable that the pressure be 30 Torr, most preferably 0.05 Torr to 10 Torr.

The substrate temperature (Tat) at the time of film formation is individually set as desired according to the type of gas used, the type of deposited film to be formed, and the required characteristics. When it is obtained, the temperature is preferably from room temperature to 450 ° C, more preferably from 50 to 400 ° C. In particular, when a silicon-based deposited film having better characteristics such as semiconductor properties and photoconductivity is formed, the substrate temperature (Ts) is desirably set to 70 to 400 ° C. When a polycrystalline film is obtained, the temperature is preferably 200 to 700 ° C, more preferably 300 to 600 ° C.

As the atmosphere temperature (Ts) of the film formation space, the precursor (E) and the precursor (F) to be generated do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently used. ) Is appropriately determined as desired in relation to the substrate temperature (Ts) so as to produce (T).

The substrate used in the present invention may be conductive or electrically insulating as long as it is appropriately selected as desired according to the use of the deposited film to be formed. As the conductive substrate, for example, Ni-Cr, stainless steel, Al, Cr, Mo, Au,
Metals such as Ir, Nb, Ta, V, Ti, Pt, and Pb and alloys thereof are exemplified.

As the electrically insulating substrate, a film or a sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamine and the like, glass, ceramic and the like are usually used. Preferably, at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is provided on the conductive-treated surface side.

For example, if it is glass, its surface is NiCr, Al, Cr, Mo, A
u, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + Sn
Conductive treatment by providing a thin film such as O ₂ ) or a synthetic resin film such as a polyester film, such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
The surface of the metal is subjected to a conductive treatment by vacuum deposition, electron beam deposition, sputtering, or the like, or by lamination with the metal.

The substrate is preferably selected from the above in consideration of adhesion and reactivity between the substrate and the film. Further, if the difference between the two thermal expansions is large, a large amount of strain is generated in the film, and a film of good quality may not be obtained. Is preferred.

Further, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the occurrence of a cone-shaped structure, it is necessary to treat the surface of the substrate so as to have a film structure having a film structure with desired characteristics. Is desirable.

As for the gas flow type in the present invention, when the raw material, the substance (D) and the oxidizing agent for forming the deposited film are introduced into the reaction space, they are uniformly and efficiently mixed, and the precursor In order for (E) to be efficiently produced and for the film to be formed appropriately without any trouble, the geometric arrangement of the gas discharge holes, the substrate, and the gas exhaust holes is determined.

In the present invention, gas discharge holes are provided on both opposing wall surfaces of the deposited film forming chamber, and the base is placed in a plane connecting these gas discharge holes. With these arrangements, the gas flow is directed to the surface of the substrate from both left and right directions around the substrate. Therefore, the deposition rate can be increased and the uniformity of the film thickness and film quality can be improved as compared with the case where the deposited film is formed from only one direction. Even if a plurality of pairs of this geometrical arrangement are provided in the same deposition film forming chamber, the effect can be sufficiently maintained as long as the planes connecting the respective gas discharge holes do not intersect. In order to improve the uniformity of the film thickness and the film quality, it is preferable that the set position of the gas exhaust hole is arranged on the wall surface facing the upper and / or lower portion of the substrate installed in the deposition film forming chamber. Of course, when a plurality of substrates are installed, it is preferable to arrange them on the wall surface facing the upper and / or lower portions of each substrate.

In the present invention, it is possible to form a multi-layer deposited film having sufficient characteristics in one deposited film forming chamber, but as described above, in order to further improve the change in interface characteristics, It is preferable to connect a plurality of deposition film formation chambers and form each deposition layer in a separate deposition film formation chamber.

In the present invention, the deposition film forming material gas has relatively little residue in the deposition film formation chamber, but remains in the previous deposition film formation chamber by changing the deposition film formation chamber for each deposition layer. The influence of the source gas for forming a deposited film can be reduced to the utmost, and the change in interface characteristics can be greatly improved.

In order to perform continuous production of an electrophotographic photosensitive device having a multilayered deposited film by the deposited film forming apparatus of the present invention,
The flow of the substrate is set so as to be in one direction. For example, first, the deposition film forming chamber of the first layer deposition film closest to the substrate,
Next, the deposition film forming chamber for the second deposition film is connected next,
Hereinafter, similarly, the deposition film forming chambers may be connected in the order of the deposition films close to the substrate, the substrate may be continuously moved, and the deposition films may be stacked. Of course, a pre-processing chamber can be connected before the first-layer deposited film forming chamber, and a post-processing chamber can be connected after the final-layer deposited film forming chamber.

Hereinafter, a deposited film forming apparatus according to the present invention will be described in more detail with reference to embodiments of the drawings, but the deposited film forming apparatus according to the present invention is not limited thereto.

FIG. 1 is a schematic top view of the deposited film forming apparatus of the present invention, and FIG. 2 is a schematic perspective view. The deposited film forming apparatus of the present invention has five cylindrical A in rectangular deposited film forming chambers 101 and 201.
l bases 102, 202, five pairs of gas ejectors 103a, 203a on the wall so as to sandwich the cylindrical Al bases 102, 202, and gas exhaust holes 105a, 2 on the wall facing the lower part of the cylindrical Al bases 102, 202.
05a, substrate heating halogen lamps 104a, 204a, reflector 104
b, 204b, and pedestals 113, 215 for transporting substrates are provided, and are isolated from the adjacent deposition film forming chambers by gate valves 111, 211. The gaseous raw material and raw material (D) pass from a cylinder (not shown) through gas supply pipes 109a and 209a and gas introduction pipes 109b and 209b, and from gas discharge holes 103c and 203c.
The gaseous oxidant is supplied from supply cylinders 110a and 210
a, gas is discharged from the five pairs of gas discharge holes 103b and 203b through the gas introduction pipes 110b and 210b toward the substrates 102 and 202, respectively, and is provided at the lower portion of the cylindrical Al substrate.
The gas is exhausted by exhaust devices 108 and 208 from a and 205a through gas exhaust holes 105 and 205a, gas exhaust pipe 205b, gas collecting exhaust pipes 106 and 206, and main vacuum valves 107 and 207.

After the film formation is completed, the substrate transfer pedestal 1 on which the substrates 102 and 202 are mounted
13,215 is the transport rail 218 in the direction of the arrow 112,212.
Is transported on

The cylindrical substrates 102 and 202 are held on a rotating jig 213, and are rotated by a driving motor 217 provided outside.
Can be rotated via 16,214.

In the present invention, in order to uniformly and stably efficiently mix the gaseous raw material and the base oxidant in the longitudinal direction, it is necessary to set the arrangement of the gas discharge holes so that each gas is discharged alternately. There is. A preferred example is shown in FIG.

Reference numerals 401a to 404a denote gas discharger bodies, and gas discharge holes 401b.
To 404b and gas discharge holes 401c to 404c (shown by oblique lines) are alternately arranged. FIG. 4 (1) shows slit-shaped discharge holes arranged in three rows, in which the gas discharge holes 401b are sandwiched by the gas discharge holes 401c. The slit width is preferably 0.01 to 50 mm, more preferably 0.02 to 30 mm, and most preferably 0.03 to 10 mm. Fig. 4 (2)
Although (1) is increased to three rows, it is effective when forming a film on a large-diameter substrate or when increasing the deposition rate. The number of slits is appropriately determined as desired.

 The slit length is appropriately determined according to the length of the base.

FIG. 4 (3) shows circular discharge holes alternately arranged in a line in the vertical direction. FIG. 4 (4) shows the circular discharge holes alternately arranged in the vertical and horizontal directions, which is effective when forming a film on a large-diameter substrate or when it is desired to increase the deposition rate. The major axis of the discharge hole is 0.01 to 100 mm, more preferably
Desirably, it is 0.05 to 50 mm, and most preferably, 0.1 to 30 mm.

The slit-shaped and circular discharge holes may be adjacent to each other or may be arranged at intervals, but it is not preferable that the intervals are set to be at least 10 times the slit width or diameter.

Regardless of the type of gas released from each of the gas release holes 401b to 404b and 401c to 404c, the film quality of the deposited film obtained does not substantially change.

In the case of the present invention, the distance between the gas release hole and the substrate surface is determined so as to be in an appropriate state in consideration of the type of the deposited film to be formed and its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, and the like. However, it is preferable that the diameter is about several mm to 20 cm, more preferably about 5 mm to 15 cm.

Hereinafter, the present invention will be described more specifically with reference to examples.

〔Example〕

An electrophotographic photosensitive device using an amorphous silicon (a-Si: H) film was manufactured using the deposited film forming apparatus of the present invention schematically shown in FIG. 1 to FIG.

In this case, the layer configuration of the electrophotographic photosensitive device was changed to the fifth layer.
Shown in the figure.

That is, the electrophotographic photosensitive device shown in FIG. 5 includes a substrate (Al) 500, an antireflection layer (first layer, a-Si: Ge: B: O: H:
F) 501, a layer for preventing charge injection from the support (second layer, P ⁺ type a
-Si: H: X: F: B: O) 502, photosensitive layer (third layer, a-Si: H: F) 5
03, surface protection layer and light absorption increasing layer (fourth layer, a-Si: C:
H: F) 504.

 Hereinafter, the manufacturing process will be described in detail.

The gas ejector used had the shape shown in FIG. 4 (1).
First, an Al cylindrical substrate 302 having a diameter of 80 mm was loaded into a pretreatment chamber 301a by opening five gate valves 311a. Exhaust device 30
After reducing the inside of the pretreatment chamber 301a to about 10 ^-3 Torr by 8a, Ar gas is supplied from a cylinder (not shown) to the gas supply pipe 309a and the gas discharge hole.
The internal pressure was maintained at 0.5 Torr by adjusting the opening of the main vacuum valve 307a. The halogen lamp 304a was turned on and the temperature of the substrate was set to 250 ° C. During that time, the base is rotated by the drive motor 217. Next, Ar
Stop the introduction of gas, from a cylinder (not shown), E ₂ gas 180SCC
M is introduced from the gas supply pipe 310a and the gas discharge hole 303a,
The substrate surface was lightly etched and cleaned. At this time, the pressure in the pretreatment chamber was kept at 0.4 Torr. The introduction of F ₂ gas was stopped, and the inside of the pretreatment chamber was evacuated to about 10 ⁻⁶ Torr. At this time,
The inside of the adjacent film forming chamber (1) 301b was simultaneously evacuated to the same internal pressure as the pretreatment chamber by the exhaust device 308b. When the internal pressures became equal, the gate valve 311b was opened, and the substrate was transferred into the film forming chamber (1) 301b while being placed on the substrate transfer pedestal 215.

After closing the gate valve 311b, the substrate heating halogen lamp 304b was turned on, and the temperature of the substrate was set to 250 ° C. After the temperature of the substrate is stabilized, a raw material for a substrate for forming a deposited film and a raw material (D) are formed from a cylinder (not shown).
SiH ₄ gas 900SCCM, GeH ₄ 240SCCM, B ₂ H ₆ (1% H ₂ dilution) 10
0 SCCM from the gas supply pipe 309b, and from a cylinder (not shown) 800 SCCM of F ₂ gas and 250 SC of NO gas as a gaseous oxidant.
CM, He gas for dilution 1400SCCM is supplied from the gas supply pipe 310b and discharged from the gas discharger 303b into the film formation chamber (1). The opening degree of the main vacuum valve 307b is adjusted, and the internal pressure is maintained at 0.7 Torr. An antireflection layer having a thickness of 0.7 μm was formed on the cylindrical substrate. After that, supply of only GeH ₄ gas was stopped and the internal pressure was continuously increased.
The charge injection blocking layer was formed at 2.4 μm while maintaining the pressure at 0.7 Torr.
After the reaction, supply of all gases was stopped, and the inside of the film formation chamber (1) was
Evacuated to 10 ^-6 Torr. At this time, the inside of the adjacent film forming chamber (2) 301c was simultaneously evacuated to the same internal pressure as the inside of the film forming chamber (1) by the exhaust device 308c. When the internal pressures became equal, the gate valve 311c was opened, and the substrate was transferred into the film formation chamber (2) 301c while being placed on the substrate transfer pedestal 215.

After closing the gate valve 311c, the substrate heating halogen lamp 304c was turned on to set the substrate temperature to 250 ° C. After the substrate temperature is stabilized, 1800 SCCM of SiH ₄ gas as a substrate material for deposition film formation is supplied from a gas supply pipe 309 c from a cylinder (not shown), and 2200 SCCM of F ₂ gas as a gaseous oxidant is supplied from a cylinder (not shown). He gas for dilution, 2500SCCM
Is supplied from the gas supply pipe 310c, and is discharged from the gas discharger 303c into the film formation chamber (2). The opening degree of the main vacuum valve 307c is adjusted to keep the internal pressure at 1.2 Torr, and the photosensitive layer is exposed on the charge injection preventing layer. A layer of 20 μm was formed. After the reaction, the supply of all gases was stopped, and the inside of the film formation chamber (2) was evacuated to 10 ^-6 Torr. At this time, the inside of the film forming chamber (3) 301d is simultaneously exhausted by the exhaust device 308d.
The vacuum was evacuated to the same internal pressure as in the film forming chamber (2). When the internal pressures became equal, the gate valve 311d was opened, and the substrate was transferred into the film formation chamber (3) 301d while being placed on the gas transfer pedestal 215.

After closing the gate valve 311d, the halogen lamp 304d for substrate heating was turned on to set the substrate temperature to 250 ° C. After the substrate temperature was stabilized, SiH ₄ gas 220SCCM, C2 was used as a substrate material for deposition film formation from a cylinder (not shown).
H41500SCCM gas supply pipe 309d, also, F ₂ gas 300SCCM as the gaseous oxidizing agent from a cylinder (not shown), the diluent He gas 1200SCCM supplied from the gas supply pipe 310 d, gas discharger deposition chamber from 303d (3) Discharge into the main vacuum valve
While adjusting the opening degree of 307d and maintaining the internal pressure at 0.7 Torr, a 0.5 μm thick surface protection and light absorption increasing layer was formed on the photosensitive layer. After the reaction, supply of all gases was stopped, and the inside of the film formation chamber (3) was
Vacuum was applied to ^-6 Torr. At this time, the inside of the post-processing chamber 301e was simultaneously evacuated to the same internal pressure as the inside of the film forming chamber (3) by the exhaust device 308e. When the internal pressure becomes equal, the gate valve
The substrate 311e was opened, and the substrate was transferred into the post-processing chamber 301e while being placed on the substrate transfer pedestal 215.

After closing the gate valve 311e, Ar
The gas 300 SCCM was supplied from the gas supply pipe 301e, released from the gas discharger 303e into the post-processing chamber 301e, and cooled until the substrate temperature reached room temperature. After the substrate temperature was sufficiently lowered, the main vacuum valve 307e was closed, the inside of the post-processing chamber 301e was purged to the atmospheric pressure with Ar gas, and the gate valve 311f was opened to take out the completed electrophotographic photosensitive device.

The electrophotographic characteristics of the five completed electrophotographic photosensitive devices were evaluated by comparing them with those of electrophotographic photosensitive devices manufactured by conventional mass-production machines. As a result, the charging ability was improved by 14% or more and the sensitivity was improved by 12% or more. Was. The characteristic unevenness in the circumferential direction and the vertical direction was 2% or less. The characteristic unevenness among the five electrophotographic photosensitive devices was 5% or less, and the performance of the deposited film forming apparatus according to the present invention as a mass production machine was sufficiently satisfied.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to the deposited film forming apparatus of the present invention, a multi-layer with a large area, a uniform thickness of a film, uniformity of a film quality sufficiently satisfied, and an improvement in interface characteristics is achieved at the same time as energy saving without a plasma reaction. Structural deposition film simplifies management and mass production, does not require large capital investment in mass production equipment, clarifies management items for mass production, wide management tolerance, easy adjustment of equipment Continuous formation becomes possible.

Specifically, (1) a large number of films can be uniformly formed at a time in a single deposited film forming apparatus, so that the apparatus cost is low.

(2) Since the flow of the gas is directed to the surface of the substrate from both left and right directions around the substrate, the uniformity of the film thickness and film quality can be improved.

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

(4) Since no external energy is required other than heating the support, the running cost of the apparatus is low.

(5) When forming a deposited film having a multilayer structure, each deposited layer can be formed with a different deposited film forming substance, so that the interface characteristics can be improved.

(6) Continuous production becomes possible by making the flow of the substrate unidirectional.

[Brief description of the drawings]

FIG. 1 is a schematic top view of a deposited film forming apparatus using an embodiment of the present invention, FIG. 2 is a schematic perspective view of the deposited film forming apparatus of FIG. 1, and FIG. FIG. 4 is a schematic top view of a continuous deposited film forming apparatus used in the embodiment, FIG. 4 is a schematic schematic view of a gas ejector used in the embodiment of the present invention, and FIG. FIG. 6 is a schematic diagram illustrating a conventional electrophotographic photosensitive device manufacturing apparatus using plasma CVD. 101, 201: deposition film forming chamber, 102, 202, 302: cylindrical substrate, 103a, 203a, 303a to e: gas discharger, 103b, 103c, 203b, 203c: gas discharge hole, 104a, 204a: halogen for heating the substrate Lamp, 104b, 204b ... Reflector, 105,205a, 305a-e ... Gas exhaust hole, 205b ... Gas exhaust pipe, 106,206,306a-e ... Gas collecting exhaust pipe, 107,207,307a-e ... Main true valve 108, 208, 308a-e ... exhaust system, 109a, 209a, 110a, 210a, 309a-e, 310a-e ... gas supply pipe, 109b, 209b, 110b, 210b, ... gas introduction pipe, 111, 211, 311a-e ... ... Gate valve, 112,212 ... Flow of substrate, 113,215 ... Receptacle for substrate transfer, 213 ... Rotating jig, 214,216 ... Rotating gear, 217 ... Drive motor, 218 ... Transport rail, 301a ... ... Pre-processing chamber, 301b ... Film forming chamber (1), 301c ... Film forming chamber (2), 301d ... Film forming chamber (3), 301e ... Post-processing chamber, 304a, 304b, 304c, 304d, 304e …… Substrate heating Halogen lamps and reflectors for use 401a to 404a gas discharger, 401b to 404b, 401c to 404c gas discharge hole, 500 substrate, 501 anti-reflection layer, 502 charge blocking layer 503: Photosensitive layer, 504: Surface layer, 611: Substrate intake room, 612: Relay room, 613: Substrate removal chamber, 614: Reactor, 615,22 ... Door, 616: Fixed substrate Jig, 617,21… Conveying means, 618… Vertical moving means, 619,20,29… Gate valve, 623… Cooling plate, 624,28… Heating heater, 630… Heating power supply, 631, 32,35,42 ... Exhaust system, 633 ... High frequency power supply, 634 ... Source gas introduction system, 636 ... Cooler, 638,39,49 ... Leak valve, 641 ... Cylindrical base.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Isamu Shimizu 2-41-21, Fujigaoka, Midori-ku, Yokohama-shi (56) References JP-A-61-6277 (JP, A) JP-A-54-125974 (JP, A) ) Japanese Utility Model Showa 57-130453 (JP, U) JP-B 60-29295 (JP, B2)

Claims (5)

(57) [Claims] An apparatus for forming a deposited film on a substrate by bringing a gaseous source material for forming a deposited film into contact with a gaseous oxidizing agent having a property of oxidizing the source material. A gaseous raw material discharge hole connected to the gaseous raw material supply pipe and a gaseous oxidant discharge hole connected to the gaseous oxidant supply pipe at positions symmetrical with respect to the base on both opposing wall surfaces. And a gas discharge hole for exhausting the deposited film formation chamber, and a deposited film forming support setting means including at least a part in a plane connecting the mixed and discharged means. A deposited film forming apparatus, wherein a plurality of installed deposited film forming chambers are connected. 2. A plurality of pairs of said mixing / discharging means, said gas discharge holes, and said deposited film forming supporting body setting means are provided in said deposition film forming chamber, and planes connecting said mixing / discharging means intersect with each other. 2. The deposition film forming apparatus according to claim 1, wherein said deposition film forming apparatus does not have any problem. 3. The deposition according to claim 1, wherein said deposition film forming apparatus is connected to a plurality of chambers in accordance with a desired number of layers of a multi-layered deposition film. Film forming equipment. 4. The method according to claim 1, wherein a pre-processing chamber and a post-processing chamber are connected in addition to the connection of the plurality of deposition film forming chambers. 3. The deposited film forming apparatus according to item 1. 5. The method according to claim 1, wherein the distance between said substrate and said mixing and discharging means is several.
The deposited film forming apparatus according to any one of claims 1 to 4, wherein the thickness is in a range of mm to 20 cm.