JPS6299463A - Deposited film formation - Google Patents

Abstract

PURPOSE:To obtain a deposited film, the quality control of which is easy, and has the homogeneous physical characteristics in a rage over a large surface by depositing the following plural precursors on a base material set in the inside of film formation space which are obtained by introducing both a gaseous raw material substance used for deposited film formation and an oxidizing agent contg. a gaseous halogen series oxidizing agent into reaction space. CONSTITUTION:Both the above-mentioned gaseous raw material substance (e.g. straight-chain and branched chain silane compds. or the like) and an oxidizing agent such as the oxygen series, nitrogen series and halogen series oxidizing agents which are made gaseous in case of the being introduced into the inside of reaction space are introduced into the reaction space. These oxidizing agents are mixed with the gas of the above-mentioned raw material substance in a gaseous state and allowed to collide each other and chemical contact is performed and the plural kinds of precursors contg. a precursor having an exciting state are produced. Thereafter these precursors are decomposed or allowed to a react and made to the precursor having other exciting state or if necessary, energy is emitted but a deposited film having a three-dimensional structure is formed by allowing them into contact with the surface of a base material arranged in film formation space in an intact form. Still further O2, O3, N2O4, H2O2, F2, Cl2 or the like can be shown as the above-mentioned oxidizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to functional films, particularly for electronic devices such as semiconductor devices, photosensitive devices for electrophotography, and optical input sensor devices for optical image input devices. This invention relates to a method for forming a functional deposited film useful for various applications.

[Conventional technology]

Conventionally, amorphous or polycrystalline functional films such as semiconductor films, insulating films, photoconductive films, magnetic films, or metal films have been developed based on their individual properties in terms of desired physical properties and uses. A film-forming method is used.

For example, if necessary, unpaired electrons can be compensated for using a compensating agent such as a hydrogen atom (H) or a halogen atom (X).

Restored amorphous or polycrystalline non-single crystal silicon (r
NON-3i (H,X)J is abbreviated as rA-3t (H,X
) J, rpo cross y when indicating polycrystalline silicon
-3i (H,X) J) film (commonly called microcrystalline silicon)
(Needless to say, it falls within the range of 100%), vacuum evaporation, plasma CVD, thermal CVD, 1 reaction sputtering, ion blating, photo-CVD, etc. have been attempted, and the general Specifically, the plasma CVD method is widely used and commercialized.

[Problem that the invention seeks to solve]

The reaction process is considerably more complicated than that of the conventional CVD method, and the reaction mechanism also has many unknown points. In addition, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure 9 reaction vessel structure, evacuation speed, plasma generation method, etc.). Due to the combination of many parameters, the plasma sometimes becomes unstable, which often has a significant adverse effect on the deposited film formed.

Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions.

In order to develop properties that fully satisfy each application, the plasma CVD method currently has a large area, uniform film thickness, and uniform film quality, and has a high f1 density. Unless a certain bankruptcy is achieved, capital investment will be required, and the management items will be complicated due to the heavy burden, the management tolerance will be narrow, and the adjustment of equipment will be delicate.
This has been pointed out as an issue that should be improved in the future.

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.

In the indirect plasma CVD method, plasma is generated using microwaves or the like at a secondary position away from the film-forming space, and the plasma is transported to the film-forming space to selectively select chemical species that are effective for film-forming. It was designed to be usable.

However, since the plasma CVD method also requires plasma transport, the lifetime of the chemical species effective for film formation must be long, which naturally limits the types of gases that can be used.
The inability to obtain various deposited films, the need for a large amount of energy to generate plasma, the generation of chemical species effective for film formation, and the inability to keep the film under easy control, etc. The problems are stacked up.

Compared to the plasma CVD method, the photo-CVD method is advantageous in that it does not generate ion species or electrons that damage film formation and film quality, but it does not have as many types of light sources, and the light source wavelength For industrial use, a large light source and its power source are required; and because the window that introduces the light from the light source into the deposition space is covered with a film during deposition, the amount of light decreases during deposition. There are still issues that need to be resolved, such as the reduction in light from the light source and the fact that the light from the light source enters the deposition space. There is a strong desire to develop a forming method that can be mass-produced. These problems can be cited as similar problems to be solved in other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

〔the purpose〕

An object of the present invention is to eliminate the drawbacks of the double deposited film formation method and at the same time provide a new method of deposited film formation that does not involve 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 provide a method for forming a deposited film that is highly productive and mass-producible, and can easily produce a film with high quality and excellent physical properties such as electrical, optical, and semiconductor properties. be.

[Means for solving problems]

The method for forming a deposited film of the present invention, which achieves the objects described in (8) above, includes a gaseous raw material for forming a deposited film, and a gaseous substrate having the property of oxidizing the raw material. It is characterized by forming.

[Effect]

According to the deposited film forming method of the present invention described in ``--, it is possible to achieve energy saving, large area, uniform film thickness, and uniform film quality, simplify management and mass production, and realize mass production equipment. It does not require a large amount of capital investment, the control items for mass production become clear, the control tolerance is wide, and equipment adjustment becomes easy.

In the method for forming a deposited film of the present invention, the gaseous raw material for forming the deposited film used is one that undergoes a liquefaction effect through chemical contact with a gaseous oxidizing agent, and is dependent on the type of deposited film desired. , are selected as desired depending on characteristics, usage, etc. In the present invention, the above-mentioned gaseous raw material and gaseous oxidizing agent may be in the gaseous state during chemical contact, and in normal cases, they may be gaseous, liquid, or solid. There is no problem.

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

Using a carrier gas such as N2 or H2, bubbling is performed while adding heat if necessary, and the raw material for forming the deposited film and the oxidizing agent are introduced in gaseous form into the reaction space.

At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous oxidizing agent are set by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material and the gaseous oxidizing agent for forming the deposited film.

In order to obtain a tetrahedral deposited film such as a thick film for forming a deposited film used in wood invention, linear and branched chain silane compounds, cyclic silane compounds, chain germanium compounds, etc. can be cited as effective.

Specifically, the linear silane compound is S in)
T2□+2 (,1=1.2,3,4,5゜6.7.8
), as the branched chain silane compound, 5iH3SiH
(SiH3)SiH2SiH3, as a chain germane compound, GemH2m+2 (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 or more.

The oxidizing agent used in the present invention is in a gaseous state when introduced into the reaction space, and at the same time it is brought into chemical contact with the gaseous raw material of the film-forming stream introduced into the reaction space. Oxygen-based oxidizing agents, nitrogen-based oxidizing agents, and halogen-based oxidizing agents are examples of oxidizing agents that have the property of effectively oxidizing.
Oxygen or nitrogen compounds such as O4, N2O3, N20, peroxides such as H2O2.

F2. Cu2. Br2. Effective examples include halogen gas such as I2, nascent fluorine, k15, and bromine.

These oxidizing agents are in a gaseous state, and are introduced into the reaction space together with the gas of the raw material for forming the deposited film at a desired flow rate and supply pressure, and are mixed and collided with the raw material to cause a chemical reaction. The raw material is brought into contact with the raw material and oxidized to efficiently generate a plurality of types of precursors including excited state precursors.

The excited state precursors and other precursors that are generated serve as a source of components for the deposited film in which at least one of them is formed.

The generated precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or is deposited in that form, although it releases energy as necessary. A deposited film with a three-dimensional network structure is created by touching the surface of the substrate placed in the space.

The excited energy level is preferably an energy level that accompanies luminescence in the process of energy transition of the excited state precursor to a lower energy level or change into another chemical species. By forming activated precursors including excited state precursors that are accompanied by light emission due to such energy transition, the deposited film forming process of the present invention proceeds more efficiently and with more energy savings.
A deposited film is formed that is uniform over the entire surface of the film and has better physical properties.

In the present invention, the ratio of the amount of the halogen-based oxidizing agent and the oxygen-based and/or nitrogen-based oxidizing agent introduced into the reaction space can be determined as appropriate depending on the type of deposited film to be created and the desired characteristics. preferably 1000/1 to 1150, more preferably 500/1 to 1/20, most preferably Zoo/1
It is desirable that it be set to ~1/10.

In the present invention, the deposited film forming process can proceed smoothly and a film having high quality and desired physical properties can be formed by controlling the type of raw materials and oxidizing agent and Ml as film forming factors.
The combination, their mixing ratio, the pressure during mixing, the flow rate, the internal pressure of the film-forming space, the gas flow type, and the film-forming temperature (substrate temperature) are appropriately 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 invention, the proportion of the gaseous raw material for forming a deposited film introduced into the reaction space and the gaseous oxidizing agent is determined in relation to the film formation factor that is intermediate among the film formation factors mentioned above. Although it can be determined as desired, the introduction flow rate ratio is preferably 17,100 to 100/l, more preferably 1,150 to 50/1.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to increase the probability of chemical contact between the gaseous raw material and the gaseous oxidizing agent, but taking into account reactivity. It is preferable to determine the optimum value as desired.

The pressure at the time of mixing is determined as described above, but the pressure at the time of each introduction is preferably I x 1
It is desirable that the pressure be 0-7 atm to 10 atm, more preferably 1X10-6 atm to 3 atm.

The pressure in the film-forming space, that is, the pressure in the space where the substrate on which the film is to be formed is disposed, is the pressure of the excited state precursor (E) generated in the reaction space and, if necessary, the precursor. The precursor (D), which is derived from the precursor (E), is appropriately set as desired so as to effectively participate in the film forming process.

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 introduction pressure and flow rate of the substrate-like raw material for forming the deposited film and the gaseous oxidizing agent in the reaction space. In relation to speed, adjustments can be made by, for example, using differential exhaust or a large exhaust system.

Alternatively, if the conductance of the connection between the reaction space and the film-forming space is small, an appropriate exhaust system may be provided in the film-forming space.
By controlling the amount of air extracted from the device, the pressure in the film forming space can be adjusted.

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 air loss as described above or use a large-sized structure with sufficient exhaust capacity. It would be better to install a loss air device.

As described above, the pressure in the film forming space is determined based on the relationship between the gaseous raw material introduced into the reaction space and the introduction pressure of the gaseous halogen oxidizing agent, and is preferably 0.00.
1 Torr -100 Torr.

More preferably 0.01 Torr to 30 Torr
, the optimum value is 0.05 to 10 Torr.

Regarding the gas flow type, when the raw material for forming the deposited film and the oxidizing agent are introduced into the reaction space, they are mixed uniformly and efficiently, and the precursor (E) is efficiently produced. It is necessary to take into consideration the geometrical arrangement of the gas inlet, the substrate, and the gas outlet when designing so that the film can be formed properly without any trouble. 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 number of types of deposited film to be formed, and the required characteristics. When obtaining , it is desirable that 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, the substrate temperature (Ts) should be 70 to 350.
It is preferable to set the temperature to ℃. In addition, when obtaining a polycrystalline film, preferably 200 to 650°C, more preferably 3
It is desirable that the temperature be 00 to 600°C.

The atmospheric temperature (Tat) in the film forming space is set such that the precursor (E) and the precursor (D) to be produced do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently heated. ) is determined as desired 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 NiCr, Steer L/S, AM, C
r, Mo, Au, I r, Nb, Ta, V, Ti, Pt
, Pd, or 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 may be NiCr, AM, or C.
r, Mo, Au, I r, Nb, Ta, V, Ti, Pt
, Pd, In2O3,5n02, ITO(I n203
+5n02) or a synthetic resin film such as a polyester film, NiCr, AM, Ag, Pb, Zn, Ni, A
u, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
The surface is conductively treated by processing with a metal such as vacuum base, electron beam evaporation, sputtering, etc., or by laminating with the metal. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined as desired.

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

101 to 108 are cylinders filled with gases used for film formation, 101a to 108a are gas supply pipes, 101b to 108b are mass flow controllers for adjusting the flow rate of gas from each cylinder, 101
c to 108c are gas pressure gauges, 101d to 108, respectively.
d and 101e to 108e are valves, 101
f to 108f are pressures 111 indicating the pressures inside the corresponding gas cylinders.

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 installed therein. The gas introduction pipes have a triple concentric arrangement structure, with a first gas introduction pipe 109 into which gas from gas cylinders 101 and 102 is introduced, and a second gas introduction pipe into which gas from gas cylinders 103 to 105 is introduced. gas introduction pipe 110 and gas cylinder 1
It has a third gas introduction pipe 111 into which gases from 06 to 108 are introduced.

Each gas introduction tube is designed to discharge gas into the reaction space so that the inner tube is located further away from the surface of the substrate. That is, the gas introduction pipes are arranged so that the outer pipes surround the inner pipes.

Gas is supplied from the tube cylinder to each introduction pipe through gas supply pipelines 123 to 125, respectively.

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

The base body 118 is installed 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. It can be determined as desired, but preferably several mm to 2
It is desirable that the length be 0 cm, more preferably about 5 mm to 15 cm.

Reference numeral 113 denotes a substrate heater that heats the substrate 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the substrate 118 to anneal the film after film formation. be.

The base heater 113 is connected to a power source 115 by a conductor 114.
Power is supplied by

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

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

Example 1 Using the film forming apparatus shown in FIG. 1, a deposited film was produced by the method of the present invention in the following manner.

Flow the SiH4 gas filled in the cylinder 101.
The F2 gas filled in the cylinder 103 is fed from the gas introduction pipe 109 at a flow rate of 20 s e cm.
From the gas inlet pipe 110 at a flow rate of 2 s e cm, the 02 gas filled in 06 is fed into the cylinder at a flow rate of 2 s e cm, and the He gas filled in the cylinder 108 is fed at a flow rate of 4140 s e cm.
Vacuum chamber 10 from gas introduction pipe 11, 1 at cm
It was introduced within 2.

At this time, the pressure inside the vacuum chamber 120 was adjusted to 100 mTorr by adjusting the opening/closing degree of the vacuum 7 large valve 119.

The substrate was stone capsule glass (the distance of 15 cm was set to 3 cm. Strong bluish light emission was observed in the mixed region of SiH4 gas, 02 gas, and F2 gas). (The body temperature (Ts) was shown for each sample. As shown in 1, the temperature was set between room temperature and 400'O.

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

Table 1 Next, Table 2 shows the film thickness of each sample when the substrate temperature was fixed at 300'0 and the flow rate of SiH4 was varied.

At this time, the gas was flowed for 3 hours for all samples. In addition, for all samples, the 02 gas flow rate was 2SCCm, the F2 gas flow rate was E￥2sec, and the He gas flow rate was 40sec.
m, and the internal pressure was 100 mTorr.

Table 2 Next, the substrate temperature was set to 300'0.5iH4 gas flow 7712
0 sec m, 02 gas flow rate 2 sccm.

F2 gas flow rate 2 sec m, internal pressure 100mTor
Table 3 shows the film thickness values of the respective samples obtained after flowing each gas for 3 hours with various He gas flow rates.

Table 3 Next, the substrate temperature was set to 300°C and the SiH4 gas flow rate was set to 20s.
Table 4 shows the film thickness values of each sample prepared by varying the internal pressure with 02 gas flow rate of 2 seconds, F2 gas flow rate of 2 seconds, and He gas flow rate of %10105e.
Shown below.

Table 4 The uneven distribution of B thickness of each sample shown in Tables 1 to 4 depended on the distance between the gas introduction tube 111 and the substrate, the flow rate of gas flowing through the gas introduction tubes 109, 110, and 111, and the internal pressure. In each film formation, by adjusting the distance between the gas introduction tube and the substrate, the unevenness in film thickness distribution could be kept within ±5% on a 15 cm x 15 cm substrate. This position corresponded in most cases to the position of maximum luminescence intensity. Si:O:H:Fll has succeeded again! i! It was confirmed from the results of electron beam diffraction that all samples were amorphous.

Also, the amorphous Si:O:H:Ftf! of each sample! A comb-shaped electrode (gap length 200 pLm) of pattern A was deposited on top to prepare a sample for conductivity measurement. Each sample was placed in a vacuum cryostat, a voltage of 100 V was applied, and a microcurrent meter (YH
P414 OB) was used to measure the current and attempt to determine the conductivity (σd), but both were below the measurement limit and the conductivity at room temperature was estimated to be 10 (4 s/cm) or less.

Example 2 Instead of introducing 02 gas in Example 1, N2O4 gas was introduced from a 107 cylinder to form a film (Sample 2).

The film forming conditions at this time are as follows.

SiH420secm F2 2secmN204
2 s c CmHe
40sec Internal pressure 100mTor
r Substrate temperature: 300° C. Distance between gas outlet and substrate: 93 cm As in Example 1, strong blue light emission was observed in the region where SiH4 gas and N2O4 gas merged.

After 3 hours of gas blowing, about 650
0 A-3i :N:O:H:F films were deposited.

It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 JLm) in A-3i:N:O:H:F film, the sample was placed in a vacuum cryostat, and the dark conductivity was measured in the same manner as in Example 1. (σd) was measured, but it was below the measurement limit.

Example 3 Instead of introducing SiH4 gas in Example 1, 10
S+2)T6 gas was introduced from the 2 cylinder to form a film (Sample 3).

The film forming conditions at this time are as follows.

Si2H620secm F2 2secm02
5sccmHe
40sec internal pressure
100mTorr base temperature 30
Distance between 0°C gas outlet and substrate: 3cm After blowing out gas for 3 hours, approximately 1.5 liters of A-5 was placed on the quartz glass substrate.
A t:O:H:F film was deposited.

It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 ILm) on the A-5t:O:H:F film, it was placed in a vacuum cryostat and the dark conductivity (σd) was measured. It was also below the measurement limit.

Example 4 Instead of introducing SiH4 gas in Example 1, 10
GeH4 gas was introduced from two cylinders to form a film (
Sample 4).

The film forming conditions at this time are as follows.

GeH420secm F2 2sccm02
2 s c cmHe
40sec Internal pressure 100mTorr Base temperature
Distance between 300°C gas outlet and base #:
After 30 m3 hours of gas blowing, about 5500 A-Ge:0:H:F films were deposited on the quartz glass substrate. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing AJJ interdigitated electrodes (gap length 200 gm) on the A-Ge:O:H:F film, it was placed in a vacuum cryostat and the dark conductivity (σd) was measured, and the results were the same as in Example 1. It was below the measurement limit.

Example 5 In addition to introducing SiH4 gas in Example 1, 10
GeH4 gas was introduced from two cylinders to form a film (
Sample 5).

The film forming conditions at this time are as follows.

SiH420sccm GeH45secm F2 3secm02
5sccmHe 4
0 sec Internal pressure 100 mTorr Substrate temperature 300°C Distance between gas outlet and substrate 3 cm After blowing out gas for 3 hours, about 7800 A-3iGe :O: H:
F film was deposited. It was confirmed by electron diffraction that this film was amorphous.

A? on the A-3iGe:O:H:F film? 7) After vacuum-depositing a comb-shaped electrode (gap length 200 gm), Sample 5 was placed in a vacuum cryostat and the dark conductivity (σd) was measured, and as in Example 1, it was below the measurement limit.

31' Example 6 Instead of introducing GeH4 gas in Example 5, 10
C2H4 gas was introduced from two cylinders to form a film (
Sample 6).

The film forming conditions at this time are as follows.

SiH420sccm C2H45secm F2 2secm02
5sccmHe 4
0sec Internal pressure 100mTorr Substrate temperature 3oo°c Distance between gas blowing date and substrate 3cm After gas blowing for 3 hours, approximately 6000 A-3I%C:O:H:F were placed on the quartz glass substrate.
A film was deposited. It was confirmed by electron diffraction that this film was amorphous.

The A −S +% C: O: H: F film J: +,
: A u After vacuum-depositing the interdigitated electrode (gap length 200 gm), Sample 6 was placed in a vacuum cryostat and the dark conductivity (σd) was measured, and as in Example 1, it was below the measurement limit.

Example 7 While introducing SiH4 gas in Example 1, 10
A film was formed by introducing Si 2H6 gas from a 2 cylinder (Sample 7).

The film forming conditions at this time are as follows.

SiH420sccm Si2H65secm F2 3secm02
5sccmHe
40sec Internal pressure 100mTorr Substrate temperature 300°C Distance between gas outlet and substrate #, 3cm After blowing out gas for 3 hours, 1.0JL of A-St :O:H:F was placed on the quartz glass substrate.
A film was deposited.

It was confirmed by electron diffraction that this film was amorphous.

A-shaped comb 33 on the A-3t:O:H:F film
- After vacuum-depositing one electrode (gap length 200p, m), sample 7
was placed in a vacuum cryostat and the dark conductivity (σd) was measured, and as in Example 1, it was below the measurement limit.

Example 8 Instead of introducing O2 gas in Example 7, N2O4 was introduced from the pump 107 to form a film (Sample 8).

The film forming conditions at this time are as follows.

SiH420sccm Si2H65secm F2 3secmN204
5sccmHe 4
0secinternal pressure 100mTorr
Substrate temperature: 300'0 Distance between gas outlet and substrate: 193 cm After 3 hours of gas blowing,
Approximately 1.0 gm of A-5i:N:O: on a quartz glass substrate.
A H:F film was deposited. The fact that this film is amorphous is due to electron beam port ・1-9
Confirmed with 4 folds.

After vacuum-depositing an A-shaped comb-shaped electrode (gap length 200 p, m) on the A-3i :N:O:H:F film-L, sample 8 was placed in a vacuum cryostat, and the dark conductivity (σd
) was measured, and as in Example 1, it was below the measurement limit.

Example 9 Instead of introducing SiH4 gas in Example 1, 10
SnH4 gas was introduced from two cylinders to form a film (
Sample 9).

The film forming conditions at this time are as follows.

S nH410s e 0m F2 5secm02
20 s c cm He
40sec Internal pressure 100rnTo
rrSubstrate temperature: 300'0 Distance between gas outlet and substrate: 4cm After blowing out gas for 3 hours, about 3000 Sn:O:H:
F film was deposited. When the film was examined by electron beam diffraction, diffraction peaks were observed, indicating that this film was of high quality.

After vacuum-depositing An interdigitated electrodes (gap length 200 pLm) on the poly-3n:O:H:F film 7, it was placed in a vacuum cryostat as in Example 1, and the dark conductivity (σ
d) were measured respectively.

The value obtained was cr d = 8 X IO-4s 7' cm.

Example 10 In Example 1, the substrate temperature was set at 600° C. and film formation was performed (Sample 10).

The film forming conditions at this time are as follows.

SiH420secm F2 2secm02
2sccmHe 4
0 sccm Internal pressure 100 mTorr Distance between gas outlet and substrate # 3 cm After 3 hours of gas blowing, approximately 500 people St:O:H were placed on the quartz glass substrate.
:F film was deposited.

When this deposited film was measured by electron beam diffraction, a diffraction peak of 5t02 was observed, indicating that it was polycrystalline.

After vacuum-depositing a pattern A comb-shaped electrode (gap length 200 gm) on the poly-5i :O:H:F film, Sample 1
0 into a vacuum cryostat, dark conductivity (σd)
When measured, it was found to be below the measurement limit as in Example 1.

Example 11 In addition to introducing F2 gas in Example 1, t and Q2 gases were also introduced from the 104 cylinder to form a film (Sample 1).
1).

The film forming conditions at this time are as follows.

SiH420sccm F2 2secmC122sc
cm Q2 2sccmHe
40sec internal pressure 1
00mTorr base temperature 300
'c Distance between gas outlet and substrate: 3 cm As in Example 1, strong blue light emission was observed in the viewing area where SiH4 gas, F2°C14 gas, and 02 gas merged. After 3 hours of gas blowing.

The fact that this film is amorphous can be confirmed by electron beam diffraction. After vacuum-depositing an electrode (gap length 200 JLm), the sample was placed in a vacuum cryostat, and the dark conductivity (σ
d) was measured, but it was below the measurement limit.

Example 12 Instead of introducing F2 gas in Example 1, C2 gas was introduced from a 104 cylinder to form a film (Sample 1
2).

The film forming conditions at this time are as follows.

5jH420sccm Cf12 2sec
m02 2sc
cmHe 4
0 sec Internal pressure 100 mTorr Substrate temperature 300° C. Distance between gas outlet and substrate 3 cm As in Example 1, strong blue light emission was observed in the region where S:iH4 gas, 0mon2 gas, and 02 gas merge. After 3 hours of gas blowing, the quartz glass film was confirmed to be amorphous by electron diffraction (gap length 2).
After vacuum evaporating 00gm), the sample was placed in a vacuum cryostat and the dark conductivity (σd) was measured in the same manner as in Example 1, but it was below the measurement limit.

〔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]

FIG. 1 is a schematic diagram of a film forming apparatus used in an example of the present invention. 101~108------------Gas cylinder, 1'01a~108 a-,------------
Gas inlet pipe, 101b to 108b----1-Mass flow meter, 101c-108c------
1------Gas pressure gauge, 101d N108d and 101e~108e------------
-Valve, 101f -108f------
--------One pressure gauge, 109, 110, 111-
--------Gas introduction pipe, 112---------
-----------One-substrate holder, 113--
--------------Heater for heating one substrate, 1
16---------Thermocouple for monitoring substrate temperature,
118-----------
--- 11 --- Substrate, 119 --- 1 -----
----------Evacuation valves are respectively represented.

Claims (16)

[Claims] (1) A gaseous raw material for forming a deposited film, a gaseous halogen-based oxidizing agent that has the property of oxidizing the raw material, and a gaseous oxygen-based and nitrogen-based oxidizing agent that has the same properties. A plurality of precursors including an excited state precursor are generated by introducing at least one of the precursors into a reaction space and making them come into chemical contact, and at least one of these precursors is deposited into a film. A deposited film forming method characterized by forming a deposited film on a substrate located in a film forming space as a supply source of constituent elements. (2) The method for forming a deposited film according to claim 1, which involves emission of light during film formation. (3) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain silane compound. (4) The deposited film forming method according to claim 3, wherein the chain silane compound is a linear silane compound. (5) The linear silane compound has the general formula Si_nH_
The deposited film forming method according to claim 4, which is represented by 2_n_+_2 (n is an integer from 1 to 8). (6) The deposited film forming method according to claim 3, wherein the chain silane compound is a branched chain silane compound. (7) The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure. (8) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound. (9) The linear germane compound has the general formula Ge_mH_
The deposited film forming method according to claim 8, which is represented by 2_m_+_2 (m is an integer of 1 to 5). (10) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound. (11) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tetrahedral compound. (12) The deposited film forming method according to claim 1, wherein the gaseous oxidizing agent is an oxygen compound. (13) The deposited film forming method according to claim 1, wherein the gaseous oxidizing agent is oxygen gas. (14) The deposited film forming method according to claim 1, wherein the gaseous oxidizing agent is a nitrogen compound. (15) Deposited film formation according to claim 1, wherein the substrate is disposed at a position opposite to the direction in which the gaseous source material and the gaseous oxidizing agent are introduced into the reaction space. Law. (16) The deposited film forming method according to claim 1, wherein the gaseous raw material and the gaseous oxidizing agent are introduced into the reaction space from a transport pipe having a multi-tube structure.