JPS62228475A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To form a deposited film having uniform characteristics with conserved energy by subjecting a gaseous raw material and gaseous halogen oxidizing agent to a reaction retarding treatment, introducing the two materials into a reaction chamber and applying heat energy thereto from a substrate to hold the materials in excited state. CONSTITUTION:After the gaseous raw material such as SiH4 in a cylinder 101 is passed through a cooling tank 125, etc., the material is supplied by an introducing pipe 109 into a vacuum chamber 120. The gaseous halogen oxidizing agent such as gaseous F2 diluted with He in a cylinder 104 is passed through a cooling tank 126, etc., and is then supplied by an introducing pipe 110 into the vacuum chamber 120. The two raw materials are cooled to the extent of avoiding the condensation so that the reaction hardly progresses by the mere contact. The heat energy is applied from the substrate 18 heated in the reaction space to the two materials to cause the contact reaction, by which the precursors in the excited state are formed. The deposited film is formed on the substrate 118 from such precursors as a supply source. The control of the film quality is made easy by the above-mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is applicable to monofunctional films, especially electronic devices such as semiconductor devices, photosensitive devices for electrophotography, pre-input sensor devices for optical image input devices, etc. Device Application 1 This relates to a method of forming a useful functional deposit n9.

[Conventional technology]

Conventionally, amorphous or polycrystalline functional films such as semiconductor films, insulating films, leading 'to+2' films, magnetic films, or gold & S films have been formed to suit each individual from the viewpoint of desired physical properties and applications. A membrane method is used.

Vacuum evaporation method, plasma CVD method, thermal CVD method, optical CVD method can be used to form the deposited film. In addition, reactive sputtering methods, ion blating methods, and the like have been attempted, and in general, plasma CVD methods are widely used and commercialized.

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 higher functionality, their electrical and optical properties and their ability to be used for edge reversing are important. There is room for further improvement in overall characteristics in terms of productivity and mass production, including fatigue characteristics, usage environment 46, uniformity, consistency, and reproducibility.

The reaction process in forming a deposit by the conventional plasma CVD method is similar to the conventional rl'i
It is considerably more complicated than the so-called thermal CVD method, and its opposite
There were also many unclear points about the 8th mechanism. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and 1 t of introduced gas, pressure during formation, high frequency power, structure of the electrode structure 2 reaction vessel, pumping speed, plasma generation method, etc.)
, due to the combination of these many parameters, the plasma becomes unstable at one time, and the formed deposit I
It often had a significant negative effect on la. Moreover, parameters unique to each device must be selected for each device, making it difficult to adapt the manufacturing conditions to a single film.

Among them, for example, amorphous silicon (It) can be formed by plasma CVD at present because it has electrical and optical properties that fully satisfy various uses. considered to be the best.

However, depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniformity of film thickness, and uniformity of film quality, and mass production with reproducibility.
The shape of the film deposited by the method shown in Table 1 requires a large amount of equipment investment for mass production equipment, the control items for the production are complicated, the control tolerance is narrow, and the adjustment of the equipment is delicate. These issues have been pointed out as issues that should be improved in the future.

Furthermore, in plasma CVD, since plasma is generated widely in the discharge space, unnecessary films or powdery products are formed in areas other than the substrate in the reactor, contaminating the inside of the reactor. Therefore, in order to obtain a high-quality deposited film, it is necessary to frequently clean the inside of the apparatus, which is a factor that reduces productivity.

On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to produce a deposited film having characteristics that are necessarily satisfactory at a commercial level.

Furthermore, although the photoCVD method is advantageous in that the reaction area can be limited to the light irradiation area, there are not so many types of light sources, and the wavelength of the light source is biased towards the ultraviolet. Requires a large light source and its power source;
Since the window that introduces the light from the light source into the deposition space is covered with a film during deposition, there is a problem that the amount of light decreases during deposition, and in the end, the light from the light source no longer enters the deposition space. .

As mentioned above, in the formation of functional films, there is a strong desire to develop a method for forming deposited films that can be mass-produced with high productivity using low-cost equipment while ensuring practical properties and maintaining uniformity. There is.

〔the purpose〕

An object of the present invention is to eliminate the drawbacks of the above-mentioned method for forming a deposited film, and at the same time to provide a new method for forming a deposited film that does not rely on conventional methods.

Another object of the present invention is to provide a method for forming a deposited film that saves energy, allows easy control of film quality, and provides a deposited film with uniform characteristics over a large area.

Still another object of the present invention is to obtain a film with excellent productivity, mass production, high quality, and excellent physical properties such as electrical, optical, semiconductor, etc. without frequent cleaning of manufacturing equipment. Another object of the present invention is to provide a method for forming a deposited film.

[Means for solving problems]

The method for forming a deposited film of the present invention which achieves the above object simply uses a gaseous raw material for forming a deposited film and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material into at least one of them. After performing a treatment to suppress the progress of the reaction, in which the reaction hardly progresses when the gases just come into contact with each other, they are introduced into the reaction space and brought into contact, and by applying thermal energy from the heated substrate, a reaction occurs near the substrate. to chemically generate a precursor in an excited state, and use the precursor as a source of the deposited film components in the deposition space. .

[Effect]

According to the uninvented deposited film forming method described in , it is possible to save energy, increase the surface area, and achieve uniformity in film thickness and quality, simplifying management and mass production, and making it suitable for mass production equipment. It does not require a large investment in equipment, the management items for its propagation become clear, the management tolerance is wide, and the adjustment of the equipment becomes easy.

Furthermore, according to the deposited film forming method of the present invention, contamination within one reaction device can be prevented and raw material gases can be used effectively, making it possible to maintain film quality and improve productivity during mass production.

[Detailed description of the invention]

In the deposited film forming method of the present invention, the gaseous raw material used for forming the deposit is oxidized by contact with the gaseous/\rogen-based oxidizing agent, and the desired deposition Types and characteristics of membranes.

It is appropriately selected depending on the purpose and the like.

In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidizing agent may be anything that is made into a gaseous state when introduced into the reaction space and brought into contact. It can be a gas, liquid, or solid. When the raw material for forming the deposited film or the halogen-based oxidizing agent is liquid or solid, use a carrier gas such as Ar, He, N2, H2, etc., and add heat if necessary.
Hebringing is performed to introduce a raw material for forming a deposited film and a halogen-based oxidizing agent into the reaction space in gaseous form.

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 semiconducting or electrically insulating silicon deposited film or germanium deposited film is to be obtained, a linear deposited film may be used. linear and branched chain silane compounds.

Effective examples include emulsion silane compounds and chain germanium compounds.

Specifically, the linear silane compound is SinH2n.
+2 (n=1.2.3,4,5゜6.7.8), as a branched chain silane compound, 5iH3SiH (SiH
3) SiH2SiH3, S as a cyclic silane compound
i nH2n (n=3.4, 5.6), and as a chain germane compound, GemH2m+ (m=1.2.3).

4.5) etc. In addition, for example, if a deposited film of tin is to be created, tin hydride such as SnH4 can be used as an effective raw material.

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

The halogen-based oxidizing agent used in the present invention is made into a gaseous state when introduced into the reaction space, and at the same time, the halogen-based oxidizing agent is used as a gas in contact with the gaseous raw material for forming a deposited film that is introduced into the reaction space. F2. CfL
2. Br2.

Halogen gas such as I2 can be cited as an effective gas.

Treatments to suppress the progress of the reaction between the gaseous raw material and the gaseous halogen oxidant include cooling the gaseous raw material and the gaseous halogen oxidant and lowering the partial pressure of the components that contribute to the reaction during the reaction. A mixture of inert gases is effective.

When cooling a gaseous raw material or a gaseous halogen oxidizing agent, the cooling temperature is such that the gases are in a gaseous state when they are introduced into the reaction space and come into contact with each other within the temperature range up to the boiling point at the atmospheric pressure. The temperature range is set so that the reaction will hardly proceed even if the substrate is in contact with the substrate, and the reaction will proceed effectively at the temperature of the substrate. Cooling methods include cooling gaseous raw materials and gaseous halogen-based oxidants through gas pipes that lead them to the reaction space in a cooling tank containing a coolant such as liquid nitrogen; There is a method of cooling by the Joule-Thompson effect by blowing the agent out from the pores into a reaction space under reduced pressure and causing adiabatic expansion.

On the other hand, when mixing inert gas with a gaseous raw material or a gaseous halogen-based oxidizing agent to lower the partial pressure of components contributing to the reaction during the reaction, the amount of inert gas to be mixed must be The amount is set to such an extent that almost no reaction proceeds, and the range is such that the reaction proceeds effectively at the temperature of the substrate.

At this time, it goes without saying that the exhaust capacity is increased depending on the amount of inert gas mixed in order to lower the partial pressure of components contributing to the reaction while maintaining the pressure within the reaction chamber within a certain range.

The gaseous raw material and the gaseous halogen oxide, which have been treated to suppress the progress of these reactions, are introduced into the reaction space with the desired flow rate and supply pressure, and come into contact during mixing and collision. The oxidation reaction takes place, but at least one side is treated to suppress the reaction, so the reaction hardly progresses at this point.In this state, the mixed gas is carried to the substrate, and the heated substrate is heated. energized,
The reaction progresses near the substrate, efficiently producing multiple types of precursors including precursors in chemically excited states. The excited state precursors and other precursors that are generated serve as a source of components of the deposited film of which at least one is formed. The precursor produced decomposes or reacts to become a precursor in another excited state or a precursor in another excited state,
Alternatively, energy is released as needed, but by touching the substrate surface in its original form, the deposited film has a three-dimensional network structure when the substrate surface temperature is relatively low, whereas it forms a crystalline deposited film when the substrate surface temperature is high. A deposited film is created.

In the wood invention, the deposition film formation process proceeds smoothly and a film with high quality and desired physical properties can be formed, and the use of raw materials and halogen-based oxidants as film-forming factors is important. The type and combination, the mixing ratio of these, the degree of treatment to suppress the reaction, the pressure during mixing, the flow rate, the internal pressure of the film forming space, the type of gas, and the film forming temperature (substrate temperature and ambient temperature) are determined as desired. Selected appropriately. 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 based on the relationship with the relevant film formation factors among the above film formation factors. The ratio of the introduced flow rate is preferably 1/20 to 100/l, and more preferably 115 to 50/1, although it can be determined as desired.

The pressure in the deposition space, that is, the pressure in the space where the substrate on which the film is to be deposited is located, is a precursor to the excited state generated in the space near the substrate by obtaining thermal energy from the substrate. The precursor (E) and, depending on the case, a precursor CD derived from the precursor (E)) are appropriately set as desired so as to effectively contribute to film formation.

The internal pressure of the film forming space can be adjusted by changing the exhaust capacity of the exhaust device in relation to the flow rates of the gaseous raw material for forming the deposited film and the gaseous halogen-based oxidizing agent.

The pressure in the film forming space as described above is determined based on the relationship between the introduced gaseous raw material and the introduction flow rate of the gaseous halogen oxidizing agent, and is preferably 0.001 Torr.
It is desirable that the pressure be ˜5 atm, more preferably 0.01 Torr to 2 atm, optimally 0.05 to 1 atm.

When the raw materials for forming the deposited film and the halogen-based oxidizing agent are introduced into the reaction space, they are mixed uniformly and efficiently, so that the precursor (E) is efficiently produced and the film formation is performed without any trouble. In order to do this properly, it is necessary to take into consideration the geometrical arrangement of the gas inlet, the substrate, and the gas outlet.

One preferred example of this geometry is shown in FIG.

The substrate temperature (Ts) 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 forming a silicon deposited film with better properties such as semiconductor properties and photoconductivity, the temperature is preferably room temperature to 450°C, more preferably 50 to 400°C. The substrate temperature (Ts) is preferably 70 to 350°C. Moreover, when obtaining a polycrystalline film, preferably 200-7^A supply 1- Ll &? ,−
1? It is preferable that l/IQQA/'1+Q convexity 00n.

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 NiCr, stainless steel, AM,
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, P
Examples include metals such as T, 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, gelatin, 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 Ni.

Cr, A, fL, Cr, Mo, Au, Ir, Nb.

Ta, V, Ti, Pt,
Pd, T n -1(') S n02,
A1Cr, An,
Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, N
The surface is treated with a metal such as b, Ta, ■, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, or the like, or laminated with the metal, thereby making the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, 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, making it impossible to obtain a high-quality film, 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.

FIG. 1 shows an example of an apparatus suitable for implementing the deposited film forming method of the present invention.

The deposited film forming apparatus shown in FIG. 1 is roughly divided into three parts: an apparatus main body, an exhaust system, and a gas supply system.

The main body of the apparatus is provided with piping for introducing gas and an external heating device.

101 to 105 are cylinders filled with gases used for film formation, 101a to 105a are gas supply vibes, 101b to 105b are flow controllers for adjusting the flow rate of gas from each cylinder, and 1o1c.
N105C are gas pressure gauges, 101d to 105 respectively.
d and 101e to 105e are valves, respectively, and 1otf to
105f is a pressure gauge that indicates the pressure inside the corresponding gas cylinder.

Reference numeral 120 denotes a vacuum chamber, which has a structure in which a pipe for introducing gas is provided at the upper part and a reaction space is formed downstream of the pipe.
It has a structure in which a film forming space is formed in which a substrate holder 112 is provided such that a substrate holder 18 is disposed. The gas introduction pipes have a double concentric arrangement structure, with a first gas introduction pipe 109 into which gas from gas cylinders 102 and 103 is introduced, and a first gas introduction pipe 109 into which gas from gas cylinders 104 and 105 is introduced. It has a second gas introduction pipe 110 to be introduced.

Each gas introduction tube is designed to discharge gas into the reaction space so that the inner tube is located farther from the surface of the base. That is, the respective gas introduction pipes are arranged so that the outer pipe surrounds the inner pipe.

Gas is supplied from each cylinder to each inlet pipe by gas supply vibe lines 123 and 124, respectively.

Reference numerals 125 and 126 are cooling tanks provided for cooling the supply gas, and are filled with a coolant such as liquid nitrogen. 125a,
125b, 126a.

126b is designed to allow bypass of the cooling tank with /Help.

Each waste introduction pipe, each gas supply vibe line, and the vacuum chamber 120 are evacuated by a vacuum exhaust device (not shown) via the main vacuum valve 119.

The base body 118 is placed at a desired distance from the position of each gas introduction pipe by moving the base body holder 112 up and down.

In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is determined appropriately by taking into consideration the type of deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. Although it can be determined as desired, it is preferably several mm to 4 mm.
It is desirable that the length be 0 cm, more preferably about 5 mm to 30 cm.

113 heats the base 118 to an appropriate temperature during film formation, or preheats the base 118 before film formation,
Furthermore, it is a substrate heating heater that heats the film in order to anneal the film after film formation.

The heater 113 for heating the substrate is connected to the power source 1 through a conductive wire 114.
Power is supplied by 15.

116 is a thermocouple for measuring the substrate temperature (Ts), and is electrically connected to the temperature display device 117.

Hereinafter, the present invention will be specifically explained according to Examples.

Example 1 Using the deposited film forming apparatus shown in FIG. 1, a deposited film was created by the method of the present invention as follows.

Close the valves 125a, 126a, close the valves 125b, 1
26b is opened to allow gas to pass through the cooling tanks 125 and 126, and the SiHaH gas filled in the pump 101 is
F2 gas diluted to 30% with He filled in the pump 104 was introduced from the gas introduction pipe 109 at a gas flow rate of 30 seconds through the gas introduction pipe 110 at a flow rate of 101005e into the vacuum chamber 120 in the cooling tanks 125 and 126, respectively. -5
It was introduced after cooling to 0°C.

At this time, the pressure inside the vacuum chamber 120 was adjusted to ITorr by adjusting the opening/closing degree of the vacuum valve 119. Gas introduction pipe 11 using quartz glass (15cm x 15cm) as the base
The distance between the tip of the 0 and the base was set to 15 cm.

The substrate temperature (Ts) was set for each sample between room temperature and 400°C as shown in Table 1.

When gas is flowed in this state for 3 hours, the film thickness of S as shown in Table 1 is obtained.
An i:H:F film was deposited on the substrate.

Furthermore, the unevenness in film thickness distribution was within ±5%. It was confirmed by electron diffraction that all of the deposited Si:H:F films were amorphous.

AM comb-shaped electrodes (
A sample for conductivity measurement was prepared based on a gap length of 200 m). Each sample was placed in a vacuum taliostat, a voltage of 100 V was applied, and a microcurrent meter (YHP4140B) was used.
The current was measured and the dark conductivity (σd) was determined. 600 again
irradiated with light of nm, 0.3 mw/cm2,
Photoconductivity (σd) was determined. Furthermore, the optical band gap (Eg opt) was determined from the absorption of light, and the results are shown in Table 1.

Comparative Example 1 Film formation was performed under the same conditions as in Example 1, except that valves 125a and 126a were opened and valves 125b and 126b were closed so that the raw material gas did not pass through the cooling tanks 125 and 126.

Strong bluish-white light emission was observed in the mixed region of SiH+ gas and F 2 /He gas, and weak near the substrate. The film deposition rate of the sample was compared with that of Example 1 when the substrate temperature was 300°C.
It was confirmed that the deposition rate of the film-like product adhering to the inner wall of the reactor was approximately three times that of C.

Table 2 shows the characteristics of each sample obtained in the same manner as in Example 1.

Example 2 A deposited film was formed by the method of the present invention in the following manner using the deposited film forming apparatus shown in FIG.

Open valves 125a and 126a, and open valves L25b and 1.
26b was closed to prevent gas from passing through the cooling tanks 125 and 126. Next, the S filled in the Pombe lot was
Pump 102 of iH4 gas at a flow rate of 30 s cm.
Ar gas filled in the chamber was introduced into the vacuum chamber 120 from the gas introduction pipe 109 at a flow rate of 270 scem. At the same time, the He gas filled in the pump 104
F2 gas diluted to 0% is fed at a flow rate of 101005e, and H e gas filled in the pump 105 is fed at a flow rate of 900se.
The gas was introduced into a vacuum chamber 8-120 at a gas introduction rate of 110 cm.

As a result, SiHaHe gas f diluted to 10% with Ar flows from the waste introduction pipe 109 at a width of 300 sccm, and F2 diluted to 3% with He flows from the gas introduction pipe 110.
11 empty Chan 8-120 at 11000 sec m
Compared to Comparative Example 1, the contribution of each introduced gas to the reaction was unchanged, but it was diluted to 1/10 with the inert residue.

At this time, the pressure inside the vacuum chamber 120 was adjusted to ITorr by adjusting the opening/closing degree of the vacuum valve 119. Using quartz glass (15cm x 15cm) as the base, waste introduction tube 11
The distance between the tip of the 0 and the base was set to 15 cm.

The substrate temperature (Ts) was set for each sample between room temperature and 400°C as shown in Table 3.

When gas was allowed to flow in this state for 3 hours, a thick Si:H:F film as shown in Table 3 was deposited on the substrate.

The film deposition rate of the sample was improved by 60% compared to Comparative Example 1 when the substrate temperature was 300° C., and the deposition rate of the film-like product adhering to the inner wall of the reactor was reduced to about 1/2. Furthermore, the unevenness in film thickness distribution was within ±5%. Film formed Si:H:F
All samples were confirmed to be amorphous by electron diffraction.

Table 3 shows the characteristics of each sample obtained in the same manner as in Example 1.

〔effect〕

From the above detailed description and examples, it is clear that according to the deposited film forming method of the present invention, a deposited film with uniform physical properties over a large area can be obtained with energy saving and easy control of film quality. In addition, it has excellent productivity and mass production, and is of high quality and electrical.
A film with excellent physical properties such as optical and semiconductor properties can be easily obtained.

[Brief explanation of drawings]

Figure 1 is a schematic diagram of the film forming apparatus of the present invention;
− is. 101~l O5------------Gas cylinder, 101a~105a------Gas introduction pipe, 101b~105b------Mass flow meter, 101c- 105c ---------- Gas pressure gauge, 101d to 105d and 101e to 105e and 125a, 125b, 126a, 126b-----
−−−−−−−−−−−−−−−−−−−−Valve, 1
01f to 105 f ---------------- One pressure gauge, 109, 110 ------------------------
--Gas introduction pipe, L 12 ---------
-----------One-substrate holder. 113 --------------Heater for heating one substrate, -1i i 6 --------- Heater pair for monitoring temperature of one substrate, 118----- −−−−−−−
---------- Monosubstrate, 119 -------
−−−−−−−−−−1 vacuum exhaust valve, 120 −
−−−−−−−−−−−−−−−−−−Vacuum Channo people−
1125, 126------------
1 cooling tank, respectively.

Claims (18)

[Claims] (1) If at least one of the gaseous raw material for forming a deposited film and the gaseous halogen-based oxidizing agent that has the property of oxidizing the raw material is brought into contact with each other, the reaction will hardly proceed. After performing treatment to suppress the progress of the reaction, it is introduced into the reaction space and brought into contact with it.
By applying thermal energy from the heated substrate, a reaction proceeds in the vicinity of the substrate to chemically generate a precursor in an excited state, and a deposited film is formed on the substrate using the precursor as a source of deposited film constituent elements. A deposited film forming method characterized by: (2) The method for forming a deposited film according to claim 1, wherein the treatment for suppressing the progress of the reaction is a treatment for cooling the gaseous raw material or the gaseous halogen-based oxidizing agent within a temperature range that does not condense it. . (3) A claim that the treatment for suppressing the progress of the reaction is a treatment for mixing an inert gas with a gaseous raw material or a gaseous halogen-based oxidizing agent to lower the partial pressure of components contributing to the reaction. The deposited film forming method according to item 1. (4) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain silane compound. (5) The deposited film forming method according to claim 4, wherein the chain silane compound is a linear silane compound. (6) The linear silane compound has the general formula Si_nH_
The deposited film forming method according to claim 5, represented by 2_n_+_2 (n is an integer from 1 to 8). (7) The deposited film forming method according to claim 4, wherein the chain silane compound is a branched chain silane compound. (8) The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure. (9) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound. (10) The linear germane compound has the general formula Ge_mH
The deposited film forming method according to claim 9, which is represented by _2_m_+_2 (m is an integer of 1 to 5). (11) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound. (12) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tetrahedral compound. (13) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen gas. (14) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains fluorine gas. (15) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas. (16) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent is a gas containing fluorine atoms as a constituent component. (17) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state. (18) The deposited film according to claim 1, wherein the substrate is disposed at a position opposite to the direction in which the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space. Formation method.