JPS6357774A - Formation of functional deposited film - Google Patents

Abstract

PURPOSE:To form a functional deposited film having various excellent characteristics on a substrate surface in a vacuum vessel with the conserved energy by introducing gaseous raw materials contg. group IV elements and gaseous halogen series oxidizing agents and further, a gaseous valence electron controlling agent at need into the vacuum vessel and bringing the same into reaction. CONSTITUTION:The conductive or nonconductive substrate 118 consisting of a metal, alloy or synthetic resin, glass, etc., is placed in the vacuum vessel 120 and is heated to 250 deg.C by a heater 113. The inside of the vacuum vessel 120 is simultaneously evacuated to about 10<-5>Torr by a vacuum valve 119. The gaseous raw materials expressed by formula [I] are supplied by an introducing pipe 109 from cylinders 101, 102 into the vacuum vessel 120, and the gaseous halogen oxidizing agents such as Cl, Br and I as the oxidizing agent thereof are supplied by a gas introducing pipe 111 into the vacuum vessel 120; further, the gaseous valence electron controlling agent contg. the group III element or group V element is supplied at need from a conduit 110 into the vessel. The amorphous deposited film having the various excellent electrical, optical and semiconductor characteristics is formed on the substrate 118 with conserved energy.

Description

Detailed Description of the Invention [Technical Field to which the Invention Pertains] The present invention relates to a film deposited on a substrate, particularly a functional film, particularly a semiconductor device, a photoreceptor device for electrophotography, a line sensor for image input, an imaging device, an optical The present invention relates to a method for forming a functional deposited film used in electromotive force devices and the like.

[Description of prior art]

Conventionally, semiconductor films, insulating films, photoconductive films, magnetic films or For amorphous to polycrystalline functional films such as metal films, a film formation method that is individually suited from the viewpoint of desired physical properties, intended use, etc. is adopted.

For example, if necessary, amorphous or polycrystalline non-single crystal silicon (rNON-3i (H
,X). Among them, rA-3i (H, y-3i (H,X)
The vacuum evaporation method is used to form silicon deposited films such as (denoted as J) films (it goes without saying that microcrystalline silicon, which is commonly referred to as microcrystalline silicon, falls within the range of A-3t(H,X)). , ion blasting method, reactive sputtering method, thermal CVD method,
There are plasma CVD methods, photo-CVD methods, and the like, and among them, the plasma CVD method has been put to practical use as the most suitable method and is generally widely known.

By the way, conventional non-single-crystal silane deposited films, such as those obtained by plasma CVD, have excellent properties and are said to be somewhat satisfactory, but even so, there are still many requirements to establish a reliable product. electrical, optical, photoconductive properties, fatigue resistance for repeated use, use environment characteristics, stability over time and durability,
Further, there is still a problem in solving the problem of satisfying all points of homogeneity.

The reason for this is that the desired functional deposited film cannot be obtained by a simple layer deposition operation, not to mention the materials used, and the process operations in particular require skilled ingenuity. However, it is large.

Incidentally, when forming an amorphous silicon (hereinafter referred to as RA SIJ) film by, for example, the so-called thermal CVD method, a silicon-based gas material is diluted, so-called impurities are mixed in, and then the film is heated at a high temperature of 500 to 650°C. Since it is thermally decomposed, precise process operations and control are required to form the desired a-3i film, which makes the equipment complex and the cost considerably high. It is extremely difficult to regularly obtain a deposited film composed of a-3t having the desired properties as described above, and therefore it is difficult to employ it on an industrial scale.

Furthermore, even with the plasma CVD method widely used for -C as described above, there are some problems in process operation and problems in equipment investment. Regarding process operations, the conditions are the thermal CV described above.
It is more complicated than method D, and is extremely difficult to form into a film. That is, for example, there are already many parameters such as substrate temperature, flow rate and flow rate ratio of introduced gas, pressure during layer formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, and plasma generation method. In addition to these parameters, there are also other parameters, and in order to obtain the desired product, it is necessary to select the exact parameters, and because the parameters are strictly selected, there are If one of the constituent factors, especially plasma, becomes unstable, the formed film will be severely adversely affected and cannot be used as a product. As for the equipment, as mentioned above, strict parameter selection is required, so the structure naturally becomes complex, and if the scale and type of equipment changes, the design must be able to accommodate the carefully selected parameters. Must. For these reasons, although the plasma CVD method is considered to be the most suitable method at present, as mentioned above, a large amount of equipment investment is required in order to mass-produce the desired silicon deposited film. However, the process control items for mass production are numerous and complex, the tolerance range for process control is narrow, and equipment adjustments are delicate, so in the end, the cost of the product becomes considerably high. There's a problem.

In addition, in the case of plasma CVD method, since plasma is directly generated by high frequency waves or microwaves in the film forming space where the substrate to be film is placed, the generated electrons and many ion species are This causes damage to the film during the film formation process, causing deterioration of film quality and non-uniformity of film quality.

An indirect plasma CVD method has been proposed as an improvement in this respect.

The indirect plasma CVD method generates plasma using microwaves or the like at an upstream location away from the film-forming space, and transports the plasma to the film-forming space to selectively use chemical species that are effective for film-forming. It was planned to be possible.

However, even in such a plasma CVD method, since plasma transport is essential, the lifetime of the chemical species effective for film formation must be long, which naturally limits the types of gases that can be used, making it difficult to form various deposited films. Problems such as the fact that plasma cannot be obtained, that it requires a large amount of energy to generate plasma, and that the generation and amount of chemical species effective for film formation cannot be easily controlled are the problems that cannot be solved. are doing.

The photo-CVD method has an advantage over the plasma CVD method in that it does not generate ion species or electrons that damage film quality during film formation, but there are not as many types of light sources, and the wavelength of the light source is also limited. It is biased toward ultraviolet light, a large light source and its power source are required for industrialization, and the window that introduces the light from the light source into the deposition space is covered with a film during deposition, so the amount of light decreases during deposition. There is a problem that the light from the light source is not incident on the film forming space.

As mentioned above, there are still many issues to be solved regarding the formation of silicon deposited films, and it is important to mass-produce them using low-cost equipment that saves energy while maintaining its practical properties and uniformity. There is a strong desire to develop a forming method that can do this.

This also applies to other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

[Purpose of the invention]

The main object of the present invention is to provide a novel method for forming a functional deposited film that eliminates the problems of the conventional deposited film formation methods described above.

Another object of the present invention is to form a film in a film forming space without using a plasma reaction, which saves energy, and at the same time, allows easy control of film quality and uniform film quality and thickness over a large area. The present invention provides a method for forming a functional deposited film that yields a deposited film of.

Still another object of the present invention is to simplify the management of film forming conditions and improve the film formation while maintaining the properties of the film formed and improving the deposition rate without using a plasma reaction in the film forming space. Excellent electrical properties that have made it easy to achieve mass production.

The object of the present invention is to provide a method for forming a functional deposited film having optical, semiconductor, and other properties.

[Structure of the invention]

The present inventors have conducted intensive research to overcome the above-mentioned problems in the conventional method for forming a functional deposited film and to achieve the above-mentioned purpose. A substance (hereinafter referred to as a "gaseous raw material") that hardly or never forms a deposited film in its energy state as it is, reacts with the substance to electronically oxidize it ( Select a gaseous substance (hereinafter referred to as a "gaseous oxidizing agent") that causes the partner atoms, ions, or molecules to lose electrons, that is, increase the oxidation number, and both are maintained at a temperature of, for example, about 300°C. They were each introduced in a gaseous state through separate routes into the film formation space where the functional deposited film forming substrate was arranged, and when they were brought into collision contact in the space above the substrate, a chemical interaction occurred between the two. As a result, a deposited film is formed extremely efficiently on the substrate surface without any formation of solid particles, and the deposited film is uniform in both thickness and quality, and has excellent electrical properties.
It was confirmed that it has optical and photoconductive properties.

After repeated research based on these confirmed findings, the present inventor found that in the above-mentioned deposited film formation method, active species generated by mixing gases introduced from different routes in the film formation space. However, since a uniform deposited film is formed on a substrate placed at an appropriate position, the method of mixing the gas, the method of transporting the generated active species, or the positioning of the substrate in consideration of the lifespan of the active species is important. It has been found that the characteristics of the deposited film are determined by factors such as: With this in mind, after repeated studies on the above-mentioned deposited film formation method, we found that the above-mentioned gaseous source material and gaseous oxidizing agent were introduced from the end of the film-forming space. Towards the base that is placed behind the gas inlet so that the introduced gas does not stagnate and faces the inlet,
It has been found that all of the introduced gaseous raw material and gaseous oxidant are uniformly released.

The present invention has been completed based on these findings, and the method for forming a functional deposited film of the present invention is based on the following formula I AaHbXc for forming a functional deposited film.・・・・・・
......I (where A is an element belonging to Group Ⅰ of the periodic table, X is a halogen element, and a, b, and c are integers that are not 0). , a gaseous halogen-based oxidizing agent having the property of oxidizing the gaseous source material, and a gaseous valence electron control agent as needed, are each introduced into the film forming space through separate routes, and both are introduced into the film forming space. A plurality of types of precursors including excited state precursors are produced by chemically contacting them without a reaction, and a small amount of these precursors (in addition, one type of precursor is used as a component of the functional deposited film). A method for forming a functional deposited film on a substrate in a film forming space as a supply source of the gaseous raw material, the gaseous halogen-based oxidizing agent, and the gaseous valence control agent, It is characterized by being introduced from the end of the film forming space.

The raw material for forming a functional deposited film used in the method of the present invention (hereinafter referred to as "raw material (A)J") is a material that hardly or never forms a deposited film in its original energy state. However, it is oxidized by chemical contact with a gaseous oxidizing agent and produces multiple types of precursors, including excited state precursors, depending on the type, characteristics, and application of the intended photoreceptive layer. The raw material t (A) of the present invention may be one that is in a gaseous state when it comes into chemical contact with a gaseous oxidizing agent, and in normal cases, it is not a gaseous one. If the raw material (A) is liquid or solid, it may be Ar or He.

Using a carrier gas such as Nz, Hz, etc., bubbling is performed while applying heat if necessary, and the material is introduced into the film forming space as a gaseous raw material (A).

The raw material (A) used in the method of the present invention is expressed by the following formula: AaHbXc .
...... (However, A is an element belonging to Group Ⅰ of the periodic table, X is a halogen element, and a, b, and c are integers other than O.), for example, In order to obtain a tetrahedral deposited film such as a semiconductor or electrically insulating silicon deposited film or germanium deposited film, linear,
Effective examples include branched chain halogenated silane compounds, cyclic halogenated silane compounds, and chain halogenated germanium compounds.

More specifically, the linear halogenated silane compound is 5iaHbXc (where a, b.

(C is an integer other than O, X is a halogen element), and the branched chain silane compound is S i H3S i F (SiH
3) As SiH, 5iHx, chain germane compounds,
GeaHbXc (However, a, b.

(C is an integer other than O, X is a halogen element), etc.

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 method of the present invention is
It is gaseous when introduced into the reaction space, and has the property of effectively oxidizing just by chemically contacting the gaseous raw material for forming a deposited film, which is also introduced into the reaction space. , Ft * C1z r Brt , 12
Useful examples include halogen gases such as

The above-mentioned gaseous raw material (A) and the above-mentioned gaseous oxidizing agent are each given a desired flow rate and supply pressure and introduced into the film forming space, and they mix and collide, resulting in chemical contact. The gaseous oxidizing agent oxidizes the gaseous raw material (A), thereby efficiently producing multiple types of precursors including excited state precursors, at least one of which is present in the supply source. This is where the photoelectric conversion layer is deposited. That is, the generated excited state precursor decomposes or reacts to become another precursor or another excited state precursor, or remains in its original form, releasing energy if necessary. By touching the surface of a substrate for forming a deposited film arranged in the film forming space, a film having a three-dimensional network structure is deposited on the substrate. In this system, the energy level of the excited precursor produced by chemical contact with the gaseous oxidant is determined by the energy transition of the excited precursor to a lower energy level or by another energy level. It is preferable that the material emits light during the process of changing into a chemical species. By forming multiple types of precursors including excited state precursors that emit light upon transition of such energy, the process of forming a functional deposited film proceeds more efficiently and with more energy savings. Uniform film thickness and film quality over the entire surface of the film, with excellent electrical properties.

A functional deposited film having optical or photoconductive properties can be formed.

The gaseous valence electron control agent used in the method of the present invention may be applied to an element belonging to Group Ⅰ of the periodic table (hereinafter simply referred to as ``Group Ⅰ element'') or an element belonging to Group V of the periodic table. A substance into which an element belonging to a group (hereinafter referred to as "group V element") can be introduced, and the group (I) element includes B, Aff
i.

Ga, In, T1, etc., and the Group V elements include N,
Examples include P, As, Sb, Bi, etc.

Specifically, in the case of forming a deposited film containing a group Ⅰ element, B z Hb is used as a gaseous valence electron control agent.
1B a HIo, BSH9, Ba)l+. ,B6H1
□, A I (CH3)3, A l (CzHs)s
, Ga(CHs)s, In(CH:+)s, etc.
Examples include compounds containing a group element as a constituent atom, and B z Hb is particularly preferred.

Similarly, when forming a deposited film containing Group V elements, PH3, P2H4, As H3, SbH: +-1B
Examples include compounds containing a Group V element such as i H3 as a constituent atom, and among them PH3 is preferred.

In the method of the present invention, the gaseous raw material (A) and the gaseous halogen-based oxidizing agent are mixed in order to smoothly proceed with the film forming process and to obtain a film of high quality and desired electrical and optical properties. Combining types, mixing ratios, pressures during mixing,
It is necessary to appropriately select the flow rate, the pressure in the film-forming space, the flow rate of carrier gas, the film-forming temperature, the flow rate of gas, etc. as desired. These various factors in film formation are organically related and cannot be determined independently, but must be determined by taking into account their mutual relationships.
For example, the ratio of the gaseous raw material (A) to the gaseous halogen-based oxidizing agent is preferably 1/100 to 1/100 in terms of the introduced flow rate ratio.
It is desirable that the ratio be 100/1, more preferably 1150 to 50/1. Furthermore, the pressure at the time of mixing the gaseous raw material (A) and the gaseous halogen-based oxidizing agent should be higher (preferably, in order to increase the establishment of chemical contact, but the pressure should be determined by taking reactivity into consideration). is preferred, preferably I Xl
It is desirable that the pressure be 0-' to 10 atm, more preferably lXl0"' to 3 atm.

Further, the pressure in the film forming space is determined based on the relationship between the gaseous raw material f (A) introduced into the reaction space and the introduction pressure of the gaseous oxidizing agent, but is preferably O,0OITor.
r~100 Torr, more preferably 0.01 Torr
~30 Torr, optimally 0.05 Torr ~10
It is desirable to set it to T orr.

Furthermore, regarding the flow rate of the gas, when introducing the gaseous raw material (A) and the gaseous oxidizing agent into the reaction space, these can be mixed uniformly and efficiently, and the precursor can be efficiently produced. In order to properly form a film without any trouble, it is necessary to take into consideration the geometric arrangement of the gas inlet, the substrate, and the gas outlet when designing.

Furthermore, the substrate temperature during film formation is set as desired depending on the type of gas used, the type of deposited film to be formed, and the required characteristics. When obtained, the temperature is preferably from room temperature to 450°C, more preferably from 50 to 400°C. In particular, when forming a silicon deposited film with better properties such as semiconductivity and photoconductivity, it is desirable that the substrate temperature be 70 to 350°C. Also, when obtaining a polycrystalline film, Preferably 200-650°C, more preferably 300-600°C
It is desirable to do so.

The ambient temperature in the film forming space is set so that the precursor to be generated and the precursor derived from the precursor do not change to something unsuitable for film formation, and the precursor is efficiently generated. It can be determined as desired in relation to the substrate temperature.

The substrate used in the method of 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. As the conductive substrate, for example, NiCr% stainless steel,
Als Cr5M o -, Aus I r S
Examples include metals such as Nb% Ta-V, Ti1Pt, and Pd, and alloys 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, ceramic, paper, etc. are usually used. Preferably, at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NiCr, AlXC
r, Mo, Au' = r r, Nb, Ta.

■, TI SP ts Pdz IntO= , 5n
ol, ITO (In2O2+5nO1), etc., or if it is a synthetic resin film such as a polyester film, N I Cr −,
A l % A g , P b % Z n % N
1% Au.

Cr, MO% I r, NbX'ra% V% Tis
The surface is treated with a metal such as Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support is
It can be of any shape, such as cylindrical, belt-like, plate-like, etc., and the shape is determined according to desire.

The substrate is preferably selected from the above in consideration of the adhesion and reactivity between the substrate and the membrane. 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, the surface condition of the substrate is directly related to the structure (orientation) of the film and the occurrence of cone-shaped structures, so it is important to treat the surface of the substrate so that it has a film structure and structure that provides the desired properties. is desirable.

Next, a deposited film forming apparatus suitable for carrying out the functional deposited film forming method of the present invention will be explained with reference to the drawings.
The present invention is not limited thereby.

FIG. 1 is a schematic cross-sectional view schematically showing an example of an apparatus suitable for the method of forming a functional deposited film of the present invention.

The apparatus shown in Fig. 1 includes a vacuum vessel equipped with a film forming chamber surrounded by earthen walls, side walls, and a bottom wall, a supply system for supplying raw material gas to the film forming chamber, and exhaust gas inside the film forming chamber. It consists of an exhaust system for

In the figure, 101 to 108 are cylinders filled with gas used for film formation, 101a to 108a are gas supply pipes, and 101b to 108b are gas flow rate adjustment from each cylinder. Mass flow controllers, 101C to 108C are gas pressure gauges, 10
1d to 108d and 101e to 108e are pulps, respectively, and 101f to 108f are pressure gauges each indicating the pressure in the corresponding gas cylinder.

Reference numeral 120 denotes a vacuum container, and a pipe for introducing gas is provided on the earthen wall, and the structure of the vacuum container is configured such that a corresponding space is formed downstream of the pipe for introducing gas, Further, a film forming space is formed in which a substrate holder 112 is arranged so that a substrate 118 for forming a functional deposited film can be placed substantially perpendicular to the flow of gas in the reaction space.

The gas introduction pipe has a concentric triple pipe structure, and from the inside, the first gas introduction pipe 109 introduces gas from the gas cylinders 101 and 102, and the gas cylinder 103.
A second gas introduction pipe 110 that introduces gas from ~105
and a third gas introduction pipe 111 for introducing gas from the gas cylinders 106 to 108. The gas discharge ports 121, which are the tips of these gas introduction pipes 109 to 111, are disposed inside the vacuum container, and the distance between the upper wall of the vacuum container and the gas discharge ports 121 can be adjusted so as to be movable as desired. ing.

Each gas cylinder 101 to 111 is connected to each gas introduction pipe 109 to 111.
Gas from 108 is transferred to gas supply pipeline 123-1
25.

Each gas introduction pipe, each gas supply pipeline and film forming space 1
20 is evacuated via a main vacuum valve 119 by an evacuation device (not shown).

By moving the substrate holder 112 up and down, the substrate 118 is adjusted so that the surface of the substrate is placed at a desired distance from the position of the gas discharge port 121.

In the case of the present invention, this base body and the gas discharge port 12 of the gas introduction pipe
The distance 1 is determined in consideration of the type of deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum container, etc., and is preferably several mm to 20 mm.
cm, more preferably about 5 mm to 15 cm.

113 is provided for heating the base 118 to an appropriate temperature during film formation, preheating the base 118 before film formation, and further annealing the film after film formation. It is a base heating heater. Power is supplied to the substrate heater 113 from a power source 115 via a conductive wire 114 .

A thermocouple 116 is provided to measure the temperature of the substrate and is electrically connected to the temperature display device 117.

〔Example〕

The method of forming a functional deposited film according to the present invention will be specifically explained using an example using the apparatus shown in FIG. 1, but the present invention is not limited thereto.

Tom'1'1 Place a quartz glass substrate (15 cm x 15 cm) on the substrate holder 112 inside the vacuum container 120! ! Place,
The distance between the substrate and the gas inlet was set to five types as shown in Table 1, and a deposited film was formed on each of these in the following manner.

First, open the main vacuum valve 119 to evacuate the inside of the vacuum container to a degree of vacuum of approximately 10-' Torr, then heat the substrate using the heater 113 until the temperature reaches 250°C, and maintain it at that temperature. did.

At this point, the Si filled in the cylinder 101
H4 gas was introduced into the vacuum vessel via the gas introduction tube 109 at a flow rate of 120 secM. At the same time, the cylinder 106 is filled with F2 diluted to 10% with Ie gas.
Gas was introduced into the vacuum vessel through the gas introduction pipe 111 at a flow rate of 200 seconds. When the flow rate of each gas becomes stable, adjust the opening and closing of the main vacuum valve 119,
The pressure inside the vacuum vessel was set at 0.45 Torr. A bluish-white light emission was observed near the gas outlet of the gas introduction pipe 109 and the gas introduction pipe 111.

When this state was maintained for 3 hours, a St:H:F film having the characteristics shown in Table 1 was deposited on the substrate 118.

In addition to stopping all gas introduced into the vacuum container, the heating heater was also stopped, and the main vacuum pulp 11
9 was opened to return the inside of the vacuum container to atmospheric pressure.

After the substrate cooled down, the substrate 118 was taken out from the vacuum container 120 and the thickness of the formed film was examined.
The unevenness in film thickness distribution was within ±5% in all cases. Furthermore, it was confirmed by electron beam diffraction that all of the deposited Si:H:F films were amorphous.

Furthermore, the substrate on which the Si:H:F film of each sample was formed was placed in another vacuum container (not shown), and S was deposited using a vacuum evaporation method.
t:H:F film with comb-shaped Al with a gap length of 200 μm
l! A electrode was deposited to prepare a sample for conductivity measurement. Each sample was placed in a vacuum cryostand, a voltage of 100 V was applied, the current was measured with a microcurrent meter (Y HP4140B), and the dark conductivity (σd) was determined. Also 600 nm,
The photoconductivity (σp) was determined by irradiating light of 0.3 mw/cm''. Furthermore, the optical band gap (Eg'') was determined by light absorption. These results are shown in Table 1.

Table 1 In addition to the gases used in Example 1, BzHh gas diluted to 1% with He gas filled in the gas cylinder 103 was introduced into the vacuum vessel via the gas introduction pipe 110 at a flow rate of 2SCCM. Si:
H:Flli was deposited, and the film quality was determined in the same manner as in Example 1.
We investigated the characteristics etc.

As a result, all the deposited films formed on the substrate were amorphous, and the results shown in Table 2 were obtained.

Table 2 [Effects of the Invention] The method for forming a functional deposited film of the present invention uses a plasma reaction instead of the conventional method of forming gas plasma by applying discharge energy or the like to a raw material gas for forming a deposited film. Therefore, it is possible to form an excellent functional deposited film without being affected by etching or other adverse effects such as abnormal discharge during film formation.

Further, the method for forming a functional deposited film of the present invention provides a method for forming a gaseous raw material for forming a functional deposited film in a film forming space and a gas having a property of oxidizing the gaseous raw material in a film forming space without using a plasma reaction. Since the photoelectric conversion layer is formed simply by introducing a halogen-based oxidizing agent, it not only saves energy but also achieves a large area, uniform film thickness and film quality, and simplifies management. Mass production becomes possible,
Furthermore, the apparatus for carrying out the method of the present invention does not require a large investment in equipment, and the management and adjustment of the apparatus is simple.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view schematically showing a typical example of a deposited film forming apparatus suitable for carrying out the method for forming a functional deposited film of the present invention. 101-108・・・・・・Gas cylinder, 101
a~108a... Gas supply pipe, 10
1b-108b... Mass flow controller, 101C-108c, 101f-108
f......Gas pressure gauge, 101d to 108d
, 101e-108e...Valve, 1
09-111... Gas introduction pipe, 112.
......Base holder, 113...
...Substrate heating heater, 114...Conductor, 115...Power supply, 116...
...Thermocouple, 117...Temperature display device, 118...Base, 119...
... Main vacuum valve, 120 ... Vacuum container, 121 ... Gas discharge port, 123
~125......Gas supply pipeline. Figure 1

Claims (3)

[Claims] (1) The following formula for forming a functional deposited film I AaHbXc・・・・・・・・・・・・・・・・・・
・・・・・・・・・I (However, A is an element belonging to Group IV of the periodic table, X is a halogen element, and a, b, and c are integers that are not 0.) A gaseous halogen-based oxidizing agent having the property of oxidizing the gaseous raw material and a gaseous valence electron control agent as necessary are introduced into the film forming space through separate routes, and both are subjected to a plasma reaction. A plurality of types of precursors including excited state precursors are produced by chemically contacting without intervening, and at least one of these precursors is used as a source of the constituent elements of the functional deposited film. A method for forming a functional deposited film on a substrate in a film forming space, the gaseous raw material, the gaseous halogen-based oxidizing agent, and the gaseous valence electron control agent being deposited in the film forming space. A method for forming a functional deposited film, characterized in that the film is introduced from the end of the film. (2) The method for forming a functional deposited film according to claim (1), wherein the gaseous raw material contains at least one of Si, Ge, and Sn as a constituent atom. (3) The gaseous raw material is F, Cl, Br and I
The method for forming a functional deposited film according to claim (1), which contains at least one type of halogen atom as a constituent atom.