JPS62149881A - Apparatus for forming deposited film - Google Patents

Abstract

PURPOSE:To permit easy control of film quality and to obtain a deposited film having uniform physical characteristics over a large area by alternately disposing plural release ports for raw materials which can be made gaseous and release ports for gaseous halogen oxidizing agents. CONSTITUTION:This apparatus for forming the deposited film introduces the raw materials which can be made gaseous for forming the deposited film from cylinders 201, 202 via an introducing pipe 223 into a vacuum chamber 222 and introduces the halogen oxidizing agent having the property to make an oxidizing effect on the raw materials from cylinders 203-205 via an introducing pipe 224 and gas distributors 210, 211 into said chamber. The gas distributors are alternately disposed with the plural release ports 210 for the raw materials and the release ports 211 for the gaseous halogen oxidizing agents. Both contact each other in the vacuum chamber 222 and chemically form the plural precursors including the precursors in the excited state. At least one of such precursors is used as the supply source for constituting the deposited film, by which the deposited film is formed on the substrate 220.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a multi-layer film, a VAI cow 4 body deno (chair, a photosensitive device for electrophotography, a 9-character image input device). The present invention relates to an apparatus for forming a functional deposited film useful for use in electronic devices such as input centimeters, devices, and electromotive devices.

[Conventional technology]

Conventionally, amorphous or polycrystalline functional films, such as semiconductor films, insulating films, photoconductive films, magnetic films, or metal films, have been formed to suit each individual from the viewpoint of desired physical W properties and applications. A membrane method has been adopted.

For forming the deposited film, vacuum evaporation method, plasma 0VDfB,
Thermal OVD method, fOVD method, reaction! Sputtering methods, ion/blating methods, and the like have been tried, and generally, plasma generators are widely used and have become commercially available.

However, since the deposited films obtained by these deposited film formation methods are required to be applied to electronic devices and optoelectronic devices that require a higher level of pumping ability, it is necessary to Fatigue characteristics during use, susceptibility to failure during use, and even uniformity.

With reproducibility of 8@, there is room to further improve the overall characteristics in terms of productivity.

What is shown in FIG. 3 is an example of a deposited film forming apparatus using a conventional plasma generator.
Reference numeral 1 denotes a film forming chamber as a film forming space, in which a desired substrate 303 is placed on a substrate support stand 302 inside.

Reference numeral 304 denotes a heater for heating the substrate, which is supplied through a conductor 305 to generate heat.

Reference numerals 306 to 309 indicate gas supply sources, which are provided depending on the type of gas of the compound containing a silicon-containing chemical compound, hydrogen, a chloride compound, an inert gas, or an impurity element. When using liquid materials in the standard state among these materials, an appropriate vaporization device is provided. In the figure, the gas supply sources 306 to 309 are marked with a, branch pipes are marked with flowmeters, C is marked with pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d or The valves marked with e are for adjusting the flow of each gas. The gas of the raw material compound is introduced into the film forming chamber 301 via the introduction pipe 310.

Reference numeral 311 denotes a plasma generator, and the plasma from the plasma generator 311 acts on the raw material gas flowing in the direction of the arrow, excites and decomposes the reacted compound, and decomposes the decomposed compound. An amorphous deposited film is formed on the base 303 by a chemical reaction. 3
12 is an exhaust pulp, and 313 is an exhaust pipe, which is connected to an exhaust device (not shown) to evacuate the inside of the film forming space.

When forming a deposited film of, for example, a-8i:H using such an apparatus, a suitable substrate 303 is placed on the support base 302, and the film is formed through an exhaust pipe using an exhaust apparatus (not shown). The inside of the membrane chamber 301 is evacuated and the pressure is reduced by %.

Next, the substrate is heated as necessary, and raw material gases such as SiH4 and SizH6 are introduced into the film forming chamber 301 from the gas supply bottle through the gas introduction f310, and the pressure inside the film forming chamber is maintained at a predetermined level. Plasma is generated in the film forming chamber 301) 7'3 by a plasma generator while maintaining the pressure to form a-8i:Hg on the substrate 303.

By the way, although conventionally deposited films obtained by Relin and plasma OVD@ are satisfactory for the time being due to their rich characteristics, there are still some issues required to establish a solid product in our section. , electrical, optical, photoconductive properties, fatigue resistance for repeated use, durability in usage environment, stability over time and durability, and homogeneity. There is still a long way to go to solve the problem of increasing the number of children.

The reason for this is that the desired deposited IR film cannot be obtained by a simple layer deposition operation, not to mention the materials used, and that special ingenuity is required in the particular process operation. The big thing is that

Incidentally, in the case of the so-called OVD method, for example, a gaseous material is diluted with so-called impurities, and then a
Since it is thermally decomposed at a high temperature of 50°C, precise process operation and control are required to form the desired deposited film, and the equipment is complicated and the cost is quite high. In such a situation, it is extremely difficult to regularly obtain a deposited film product that is homogeneous and has the desired custom features as described above, and therefore is difficult to employ for industrial film formation.

Furthermore, even with the plasma generation method, which is generally widely used as an optimal method, as mentioned above, there are some problems in process operation and problems in equipment placement. Regarding the process operations, the conditions are the OV mentioned above.
It is more complicated than method D, and is extremely difficult to form into a film. In other words, consider the interrelationship parameters among basic temperature, flow rate and flow rate of introduced gas, pressure during layer formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, and plasma generation method. There are already many parameters, and there are other parameters as well, and in order to obtain the desired product, it is necessary to select the exact parameters, and even though the parameters are strictly selected, Therefore, one of the constituent factors, especially the source, is plasma, and if the unstable state is maintained, the formed film will be severely adversely affected and cannot be used as a product. As for the equipment, as mentioned above, it is necessary to select strict parameters, so the structure is naturally complicated, and the equipment size and
If the weight class changes, it is not necessary to set it so that it can correspond to the individually selected parameters.

When it comes to plasma CVD,
Although this is considered to be the optimal method at present, from the above-mentioned point of view, if the desired deposited film is to be obtained, a large amount of capital investment will be required for the equipment, and in such a case, it is difficult to obtain the desired deposited film. The process/accounting items for production are many and complex, the process control tolerance range is narrow, and the equipment,...
4. Because the adjustment is delicate, the introduction office will force the product) 7.1″
There are problems such as making it expensive to recycle.

In addition, the various devices mentioned above have diversified, and the element materials for them, that is, the above-mentioned smoking characteristics, etc., must be added together, and appropriate to the applicable target and use.
In some cases, there is a social demand for a steady supply of stable semi-planted products at a low cost, and the development of methods and devices that meet this demand is urgently needed. There are situations where this is the case.

[Purpose of the invention]

The present invention solves the above-mentioned problems with respect to conventional apparatuses for forming deposited films used in photovoltaic elements, conductor devices, line sensors for image input, photographic devices, photosensitive devices for electrophotography, etc. The purpose is to meet the requirements of

That is, the main object of the present invention is to provide a material whose '6fE optical, optical, and photoconductive properties are substantially always stable regardless of the usage environment, and which has excellent resistance to light fatigue. A deposited film for forming an improved deposited film that does not deteriorate even after repeated use, has excellent durability and moisture resistance, and is uniform and homogeneous without causing residual potential problems. The purpose of the present invention is to provide a forming device.

Another object of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film uniform and homogeneous, while making it suitable for large-area films and improving film productivity. It is also an object of the present invention to provide a deposited film forming apparatus that can be easily operated directly.

[Structure and effect of the invention]

As a result of extensive research in order to overcome the aforementioned problems with conventional devices and achieve the above-mentioned objectives, the present inventor has discovered a raw material that can be made into a gaseous state for forming a deposited film, and a material that can be oxidized into the raw material. A precursor in an excited state is chemically generated by introducing a gaseous halogen-based oxidant having the property of acting into the reaction space and bringing it into contact, and the precursor is supplied to the constituent elements of the deposited film. We have developed an A-direction method that can efficiently form a desired deposited film over a large area while maintaining uniformity in film thickness and film quality on a substrate located in a film formation space as a source.

That is, the method of the present invention is to react a raw material 1, which can be made into a gaseous state for use in pickling and dusting, with a gaseous ROGE/system relative agent that has the property of oxidizing the raw material. This device efficiently mixes these gases when they are brought into contact with each other in the space, and generates the precursor necessary for forming a deposited film over a large area. The shape of the gaseous halogen-based oxidizing agent discharge port and the gaseous halogen-based oxidizing agent discharge port are circular, oval, or slit-shaped, and are arranged in one row in the horizontal direction, in multiple rows in the horizontal and vertical directions, or in multiple rows radially. , the device is characterized in that its material is metal, resin, or ceramic.

11X, which can be made into a gas for forming the deposited film of the present invention, and a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material are introduced into the reaction space. When the outlet is circular, it is determined as appropriate depending on the relationship between film-forming factors such as the distance to other adjacent discharge ports, the flow rate of the raw material and halogen-based oxidizing agent, and the pressure in the reaction space. Its diameter is preferably 0. It is desirable that the length is O1 to 110011L, more preferably 0.05 to 50m, and optimally 0.1 to 201m.

Similarly, if the outlet is elliptical, its geometric diameter is preferably 0.01 to 50tttx, more preferably 0.
．． 05 to 20, optimally 0.1 to 10, power)
The length ratio (R/L) of the short axis (81) and the long axis (L) is preferably 1/1 to 1/10000°, more preferably 1/1
It is desirable that it be 2 to 1/1000. Similarly, when the discharge port is slit-shaped, the slit width is preferably 0.01 to 501 I1 m1, more preferably 0.05 to 501 m1.
It is desirable to set it to 20 tom, optimally 0.1 to 10 tom. The length of the slit is preferably at least one rhyme, more preferably at least 5 rrm, and optimally at least 10 rhymes.

In the present invention, a gaseous material for forming a deposited film is introduced into the reaction space, and a gaseous halogen-based oxidizing agent that oxidizes the material is introduced into the reaction space. When the outlets are arranged in one row in the horizontal direction, or in zero rows in both the horizontal and vertical directions, the distance between adjacent outlets is determined by the flow of the raw material or halogen-based oxidizer J! The distance between the ends of the discharge ports is preferably 50 mm or less, more preferably 20 mm, although it is determined as appropriate depending on the relationship between film forming factors such as the pressure within the 1'1 reaction nitrogen chamber.
It is desirable that it be less than mrtt, most preferably less than 10+i. In the case of radial arrangement, it is desirable to arrange at least two or more rows, preferably three or more rows outward from the center, and three or more rows, preferably four or more rows in the circumferential direction.

In the present invention, when the material of the discharge port used is metal, stainless steel, Alp Or, MoI, etc.
Au gPt, Nb, Ta, V, Ti, Fe, Pd, N
When it is a resin such as i-0r, it is polyester or polyethylene.

kl for ceramics such as polycarbonate, cellulose acetate, polypropylene/, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc.
z Ox t S 10Ht B e Ot MgOt
ZrOz, SiO, Tie, ZrO, BN, AJN,
Examples include Si3N4. Preferably, Al or stainless steel is used from the viewpoint of workability, corrosion resistance, etc.

In the present invention, when a plurality of gas discharge ports are arranged, in order to improve the gas mixing ratio, the gas seeds discharged from the various discharge ports are arranged alternately and regularly, or
It may be emitted in multiple groups such as one, three, or irregularly.

Since the apparatus of the present invention has no chance of generating electrical discharge in the film forming space, that is, the reaction chamber, the deposited film formed is free from ion damage and other undesirable effects such as abnormal electrical discharge action. I never receive it.

According to the deposited film forming apparatus of the present invention, it is possible to save energy, simultaneously increase the area, uniform film thickness, and uniform film quality, simplify management, and achieve mass production. There is no need for a large amount of capital investment in the equipment, and the management items for the IL-production become clear, the management tolerance range is wide, and the adjustment of the equipment becomes easy.

In the deposited film forming apparatus of the present invention, the raw material used for forming the deposited film, which can be made into a gas, is oxidized by contact with the gaseous halogen-based oxidizing agent, so that the desired deposited film cannot be formed. type, e-sexuality.

It is appropriately selected depending on the purpose and the like. In the present invention, the above-mentioned raw materials and gaseous halogen-based oxidizing agents that can be made into a gaseous state may be ones that are made into a gaseous state when they are introduced and brought into contact. It does not matter if it is liquid or solid.

Ar or He when the raw material for forming the deposited film or the halogen-based oxidizing agent is liquid or solid.

Using a carrier gas such as NZ, H2, etc., and applying heat if necessary, vaporization is performed to introduce a raw material for forming a deposited film and a halogen-based oxidizing agent into the reaction space in a gaseous state.

At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidizing agent can be adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous halogen-based oxidizing agent. Set.

As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral deposited film such as a semiconductor or electrically insulating silicon deposited film or germanium deposited film is to be obtained, linear Effective examples include linear and branched chain silane compounds, cyclic silane compounds, and chain germanium compounds.

Specifically, as a linear silane compound, 81 nH2
n +2(n-1# 2p 3p 4t 5p 6#
7p 8), as a branched chain silane compound, 8
iH1SiH(S iH3) S iHI S iHl
% As a cyclic silane compound, 5inH2n(n-
3,4,5,6), as a chain germane compound, Oe
Examples include mHl m+2 (m-1, 2, 3r 45). In addition, for example, tin hydride such as SnH4 can be used as an effective raw material for forming a deposited film of tin.

Of course, these raw materials can be used not only alone, but also as a mixture of two or more.

The halogen-based oxidizing agent used in the present invention is in a gaseous state when it is introduced into the reaction space, and the halogen-based oxidizing agent is in a gaseous state when it is introduced into the reaction space, and the halogen-based oxidizing agent is in a gaseous state when it is introduced into the reaction space. It has the property of effectively oxidizing, and F2
*Halogen gas such as Ols e Brl t x, nascent fluorine, chlorine, bromine, etc. can be cited as effective.

These halogen-based oxidants are in a gaseous state, and are introduced into the reaction space together with the gaseous raw material for forming the deposited film at a desired flow rate and supply pressure, where they mix and collide with the raw material. By doing so, the raw material is oxidized to efficiently generate a plurality of types of precursors including excited state precursors. The excited state precursor and other precursors that are generated serve as a source of components of the deposited film, at least one of which is formed.

The produced precursor may be decomposed or reacted to form another excited state precursor or a precursor in another excited state, or it may be formed in its original form, releasing energy as required. By touching the surface of the substrate disposed in the membrane space, when the substrate surface temperature is relatively low, a deposited film with a three-dimensional network structure is created, and when the substrate surface temperature is high, a crystalline deposited film is created. Ru.

In the present invention, the type of raw material and halogen thread thinning agent as film-forming factors are selected so that the deposited film forming process can proceed smoothly and a film having high quality and desired physical properties can be formed. The mixing ratio, the pressure during mixing, the flow rate, the internal pressure between the film forming windows, the gas flow type, and the film forming temperature (substrate temperature and ambient temperature) are selected as desired. These film-forming factors are organically related and are not determined independently, but are determined depending on each other in relation to each other. In the present invention, the ratio of the amounts of the gaseous raw material for forming a deposited film and the gaseous halogen-based oxidizing agent introduced into the reaction space is determined depending on the relationship with the relevant film-forming factors among the above-mentioned film-forming factors. Although it is determined according to the desired ratio, the introduction flow ratio is preferably 1/20 to 100/1, more preferably 115 to 50/1.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to increase the contact between the gaseous raw material and the gaseous nitrogen-based oxidizing agent more than the probability f.
Optimal 1111' depending on the desired I considering the reactivity.
i- It is better to decide. The pressure of the mixed 1 temple is as follows:
Although determined as described above, it is desirable that the pressure at the time of each introduction is preferably I x 10-' atm to 5 atm, more preferably lXl0"' to 2 atm.

The pressure in the film-forming space, that is, the pressure in the space on which the substrate on which the film is to be formed is disposed, is the same as the excited state precursor (E) generated in the reaction space and in case I. The precursor (D) derived from the precursor (E) is appropriately set as desired so as to effectively contribute to film formation.

When the film forming space is open and continuous with the reaction space, the internal pressure of the film forming space is determined by the pressure in the reaction space between the substrate-like raw material for forming the deposited film and the gaseous nitrogen-based oxidizing agent. In relation to the introduction pressure and flow rate, adjustments can be made by, for example, using differential exhaust or a large exhaust device.

Alternatively, if the conductance of the connection between the reaction space and the film-forming space is small, the pressure in the film-forming space can be adjusted by installing an appropriate exhaust system in the film-forming space and controlling the exhaust volume of the exhaust system. I can do it.

In addition, if the reaction space and film-forming space are integrated and the reaction position and film-forming position are only spatially different, use differential pumping as described above or use a large-scale pump with sufficient exhaust capacity. It is best to install an exhaust system.

As described above, the pressure in the film forming space reacts! It is determined based on the relationship between the gaseous raw material introduced between I and the introduction pressure of the gaseous halide oxidizing agent, but preferably 0.0
OITorr ~ 100Torr, more preferably 0
．． 01Torr~30Torr, optimally ha o, o
It is desirable to reduce the pressure to 5 to 10 Torr.

Regarding the original form of the gas, when the raw materials for implantation formation and the halogen-based oxidizing agent are introduced into the reaction space, they are evenly and efficiently mixed, and the precursor (E) It is necessary to take into consideration the geometrical arrangement of the gas inlet, the silkworm body, and the gas exhaust port so that the gas can be efficiently generated and the film can be formed properly without any problems. Specifically, it is preferable that the substrate be disposed at a position opposite to the direction in which the gaseous substance and the gaseous halogen-based oxidizing agent are introduced into the reaction space.

The substrate temperature (+1+ s) during film formation is set as desired depending on the type of gas used, the i number of the deposited film to be formed, and the required characteristics. When a film is obtained, the temperature is preferably reduced from room temperature to 450°C, more preferably from 50 to 400"C.

In particular, crystalline sediments with better properties such as semiconductivity and conductivity! When forming an R film, the substrate temperature (Ts) is 30
It is desirable to set it to 0-700''0.

The atmospheric temperature (Ta t ) in the film-forming space is set so that the precursor (B) and the precursor (D) to be produced do not change into a chemical strain unsuitable for film-forming, and the precursor (Ta t ) is efficiently controlled. B
) is appropriately determined in relation to the substrate temperature (Ts). .

The substrate used in the present invention may be electrically conductive or electrically insulating, as long as it is appropriately selected depending on the intended use of the deposited film to be formed. Examples of the conductive substrate include Ni0r, stainless steel, A7
, Or, Mo, Au.

Ir, Nb, Ta, V, 'IJ, Pt,
Examples include metals such as Pd and metals thereof.

As the electrically insulating substrate, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, etc. are usually used. Preferably, at least one surface of these electrically insulating substrates is subjected to conductive treatment, and another layer is preferably provided on the surface that has undergone conductive treatment.

For example, in the case of glass, its surface or Ni Or.

Person A! , Or, Mo, Au, Ir, Nb, Ta, VT
ig P t p P d p I n! On t
S" 02 y I'l 0(Inn's +8
conductive treatment by providing a thin film such as nO*)
Or if it is a synthetic resin film such as polyester film, N iOr? Al! tAg, Pb,
Zn, Ni, Au, Or,
Mo, Ir.

The surface is treated with a metal such as Nb, Ta, V, Ti 2 , Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, thereby making the surface conductive.

The shape of the support is cylindrical.

Belt-like, plate-like, arbitrary shape]--as desired,
The co-substrate whose shape is determined is preferably selected from among the above, taking into consideration the adhesion and reactivity between the substrate and the substrate. Furthermore, if the difference in thermal expansion between the two is large, a large amount of distortion will occur in the film, and a high-quality film may not be obtained, so select and use a substrate with a close difference in thermal expansion between the two. is preferable.

In addition, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the occurrence of cone-shaped structures, it is necessary to adjust the g
It is desirable to treat the second side of the substrate for the structure and membrane structure. In order to increase the uniformity of film quality and film thickness, the substrate is rotated within the film forming space in addition to using the gas outlet according to the present invention.

*Additional effects such as vibration can also be added.

Hereinafter, the deposited film forming apparatus of the present invention will be explained with reference to the embodiments shown in the drawings.
Although this will be explained in detail below, the deposited film forming apparatus of the present invention is not limited thereto.

Figures 1 (1) to (12) show a raw material for forming a deposited film that can be made into a gaseous state and a gaseous material that has the property of oxidizing the raw material, which is used in the deposited film forming apparatus of the present invention. This is a schematic diagram when viewed from the discharge port side when the discharge ports for the halogen-based oxidizing agent and the halogen-based oxidizing agent are arranged alternately. It shows.

In Figures 1 (1) to (12), 101 is a discharge port for a raw material that can be made into a gas for forming a deposited film, and 102 is a discharge port for a gaseous oxidizing agent. They are arranged alternately as indicated by white blanks and diagonal lines. However, 101 is a gaseous halogen oxidant outlet, 102
0103 is the distance t1 between the end R of the discharge port 101 and the discharge port 102, which essentially does not change the film quality of the deposited film that is obtained as a discharge port for the raw material that can be made into a gaseous state for deposition. It represents.

Fig. 1 (1) shows the case where circular objects are arranged horizontally in a row with a good gap l 'f; Fig. 1 (2) shows the case where circular objects are arranged horizontally in a horizontal row with a distance of 103. t, 13) is shown in Figure 1 (4
) is the case when elliptical objects are arranged horizontally in a row with a distance of 103, Fig. 1 (5) is the case when slit-like objects are arranged vertically without gaps, and Fig. 1 (6) is the case when slit-like objects are arranged horizontally in a row with a distance of 103. If objects are arranged vertically with a distance of 10:3, the first
Figure (7) shows circular objects arranged radially at a distance of 103, Figure 1 (8) shows circular objects arranged radially, and Figure 1 (9) shows circular objects arranged radially. distance 1
03 and the gas emitted in the circumferential direction is arranged differently. Figure 1 Ql shows the case where slit-shaped ones are arranged radially, and Figure 1 (11) shows the case where circular ones are arranged vertically. FIG. 1 (12) shows a case where slit-like objects are arranged without any gaps in the horizontal direction.

The example shown here is just one example, and the arrangement of the outlets can be varied depending on the desired size of the substrate.

The deposited film forming apparatus shown in FIG.
It is broadly divided into three types: gas supply system and gas supply system.

The apparatus main body is provided with a reaction space and a film forming space.

201 to 105 are cylinders filled with gas used in film formation, 201a to 205a are gas pipes, and 201b to 205b are mass flow controllers for adjusting the flow rate of gas from the valley cylinders, respectively. , 20
%c~205c is the same gas pressure gauge, 201d~
2054 and 201e to 20'F+e are pulps, respectively, and 20f to 20'%f are pressure gauges that indicate the pressure inside the gas cylinders, respectively.

2) Reference numeral 2 denotes a vacuum chamber, which has a structure in which a piping for introducing gas is provided at the upper part and a reaction space is formed downstream of the piping.
) 0 is installed, and has a structure in which a film forming space is formed in which a substrate holder 214 is provided. The piping for gas introduction has the arrangement structure of chair 1 shown in FIG.
It has a first gas introduction pipe 213 into which the gas from the gas cylinders 203 to 205 is introduced, and a second gas introduction pipe into which the gas from the gas cylinders 203 to 205 is introduced. The tubes are arranged alternately.

Gas 11a is supplied to each inlet pipe.
The gas is distributed by the big lines 2) 3, 2) 4, further distributed by the gas distributors 210, 211, and led to the respective gas introduction pipes.

Each gas introduction pipe, each gas supply vibrator/and vacuum chamber 2) 2 is evacuated by a vacuum evacuation device (not shown) via a main Jc nitrogen valve 2) 1.

By moving the substrate holder 214 up and down, the substrate 2) 0 is placed at a desired distance from the position of each gas introduction pipe.

In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is determined by taking into account the type of deposited film to be formed and its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. State l yells. It can be determined as desired, but preferably several mm
~20cIIL, more preferably 5 myn-15CI
It is desirable to set it to tLgK.

215 is used to heat the base 2) 0 to an appropriate temperature during film formation, or to heat the base 2) 0 before film formation, or to anneal the film after film formation. This is a heater for heating the substrate that heats up to 7J11.

The base body heater 215 is supplied with electric power by a 11t pipe 217 via a conductive wire 216 .

218 is a thermocouple for measuring the t temperature of the substrate temperature (Ts), and is electrically connected to the temperature fluctuation indicator 219.

The present invention will be specifically described below in accordance with the real IA sequence.

Example 1 Modeling shown in Figure 2! A deposited film according to the method of the present invention was prepared in the following manner using d.

The gas discharge ports are of the type shown in Fig. 1 (1), arranged in a horizontal row f, and the gas inlet pipes 212, 213 are circular in shape and have a diameter of 5 myin, and are arranged in a horizontal row 651 times. There is.

S iH4 waste stream i2 filled in cylinder 201
F2 gas f a 1z 5 s CCQI is filled into cylinder 203 from gas 4 input 213 at 0sec.
, the flow of He gas filled in the cylinder 204 ■20s
ECM was introduced into the vacuum chamber 2) 2 through the gas introduction pipe 212.

At this time, the pressure of the A empty chamber/bar 2) 217'i was adjusted to 0.9 Torr by adjusting the opening/closing degree of the vacuum pulp 2) 1. The base is made of quartz glass (30crILX 1cTL), and the distance between the gas inlets 212, 213 and the base is 3ci.
It was set to A strong white luminescence was observed in the mixed area of SiH4 gas and F2 gas. Substrate temperature (T's) is 250''O
I set f.

When gas was allowed to flow in this state for 3 hours, a Si:H:F film having a thickness of T shown in Table 1 was deposited on the substrate.

Moreover, the unevenness in film thickness distribution was suppressed to 3% or less in both the vertical and horizontal directions. The characteristics were also uniform. Film-formed Si:
H: The I-film was found to be amorphous by electron plate diffraction.

Al comb-shaped electrodes (gap length 200 μm) were deposited on this amorphous s b ::H::F + film to prepare a sample for isoelectric constant measurement. Place each sample in a vacuum cryostat, apply a heavy pressure of 100 V, and use a microcurrent meter (Y) JP.
4140B), and the dark conductivity (d) was determined.The source of 0 or 600 nm, 0.3 mw/crtt was irradiated to determine the photoconductivity (σp). Target bandgap (Eg opt) f-metal.

These results are shown in Box 1.

Example 2 to Step 2 The same film forming apparatus as in Example 1 was used, the gas flow rate, pressure, etc. were kept constant, and the gas discharge ports were of the shapes shown in Figures 1 (2) to (12), respectively. 4. Using the dimensions shown below,
The substrate was made of quartz glass and had the dimensions shown in Tables 1 to 3 to form deposited films.

The results are shown in Tables 1 to 3.

A deposited film with very uniform thickness and properties over the entire surface of the substrate was obtained.

〔effect〕

From the above detailed description and each example, it is clear that the deposited film forming apparatus of the present invention saves energy, makes it easy to control film quality, and allows deposited films with uniform physical properties to be formed over a large area. Ru. In addition, it is possible to easily obtain a film that is excellent in reproductive performance, mass production, high quality, and excellent physical properties such as electrical binary and semiconducting properties.

Ru.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a discharge port for a raw material and a halogen-based oxidizing agent used in the Fu IM chestnut of the present invention. FIG. 2 is a schematic diagram of a film forming apparatus used in an example of the present invention. FIG. 3 is a schematic diagram of a film forming apparatus using a conventional plasma generating apparatus. 101.102... Distance between raw material purchase outlet that can be made into a gas and gaseous halogen oxidizer outlet 103... Distance of outlet IMj 201-205... Gas guide/pe 201a-205a... Gas Introduction of 201b~20
5b...Mass flow meter 201c-205c...
Gas pressure gauges 201d to 205d, 201e to 205e...
・Pulp 201f to 205f...Pressure gauge 210.211...Gas distributor 212.213...Gas gas pipe 214...Substrate holder 215...Substrate heating heater 216...4 Kneading 217 ... Tun Gap 218 ... Basic temperature motor dedicated pair "S19"
... Temperature display device 2) 0 ... Substrate 2) 1 ... Evacuated pulp 2) 2 ... Vacuum chamber 302 ... Substrate support crushing 303 ... Substrate 304 ... Bottle heating Heater 305... Conductor wires 306 to 309... Gas supply source a... Branch pipe b... Flow type C... Pressure gauges d, e... Pulp 310... Raw material gas introduction... g 311 ... plasma generator 312 ... exhaust pulp 313 ... exhaust gas g. Appearing person: Gyanon Nishi Company No. 10, Figure 1

Claims (6)

[Claims] (1) A raw material that can be made into a gas for forming a deposited film and a gaseous halogen-based oxidizing agent that has the property of oxidizing the raw material are introduced into a reaction space and brought into contact with each other to form an excited state. chemically producing a plurality of precursors including a precursor;
In a deposited film forming apparatus that forms a deposited film on a substrate in a film forming space by using at least one of these precursors as a supply source of deposited film constituent elements, the discharge port for the raw material that can be made into a gaseous state is provided. and a plurality of discharge ports for the gaseous halogen-based oxidizing agent are arranged alternately. (2) The deposition according to claim 1, wherein the outlet for the source material that can be made into a gas and the outlet for the gaseous halogen-based oxidant have a circular, elliptical, or slit shape. Film forming device. (3) Deposited film formation according to claim 1, wherein the discharge ports for the raw material that can be made into a gas and the discharge ports for the gaseous halogen-based oxidizing agent are alternately arranged in a row in the lateral direction. Device. (4) The deposited film according to claim 1, wherein a plurality of discharge ports for the raw material that can be made into a gas and a plurality of discharge ports for the gaseous halogen-based oxidizing agent are arranged alternately in the horizontal and vertical directions. Forming device. (5) The deposited film forming apparatus according to claim 1, wherein a plurality of discharge ports for the source material that can be made into a gas and a plurality of discharge ports for the gaseous halogen-based oxidant are alternately arranged in a radial manner. (6) The material of the outlet for the raw material that can be made into a gas and the outlet for the gaseous halogen-based oxidizing agent is metal, resin,
The deposited film forming apparatus according to claim 1, which is a ceramic surface.