JPH0645883B2 - Deposited film formation method - Google Patents

Description

The present invention relates to a functional film, in particular, an electronic device such as a semiconductor device, a photosensitive device for electrophotography, an optical input sensor device for an optical image input device, and the like. The present invention relates to a method for forming a functional deposited film useful for an application.

[Conventional technology]

Conventionally, an amorphous or polycrystalline functional film such as a semiconductor film, an insulating film, a photoconductive film, a magnetic film, or a metal film is individually formed from the viewpoint of desired physical characteristics or intended use. The method has been adopted.

For example, amorphous or polycrystalline non-single-crystal silicon (hereinafter referred to as "NON-Si (H)" in which unpaired electrons are compensated with a compensating agent such as a hydrogen atom (H) or a halogen atom (X), if necessary. ，
X) ”, and in particular,“ A—Si (H, X) ”indicates amorphous silicon, and“ poly-Si (H, X) ”indicates polycrystalline silicon. A silicon deposited film such as a film (the so-called microcrystalline silicon is
Needless to say, it does not fall into the category of A-Si (H, X)) for forming a vacuum deposition method, a plasma CVD method, a heat C method.
The VD method, the reaction sputtering method, the ion plating method, the photo CVD method, and the like have been tried, and generally, the plasma CVD method is widely used and commercialized.

[Problems to be solved by the invention]

However, the reaction process in the formation of a silicon-based deposited film by the plasma CVD method which has been generally generalized is
It is considerably complicated as compared with the conventional CVD method, and its reaction mechanism is often unknown. In addition, there are many parameters for forming the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, forming pressure, high frequency power, electrode structure, reaction vessel structure, exhaust speed, plasma generation method, etc.). Due to the combination of many parameters, the plasma was sometimes in an unstable state and had a considerable adverse effect on the formed deposited film. In addition, the parameters peculiar to the device must be selected for each device, which makes it difficult to generalize the manufacturing conditions.

On the other hand, in order to develop a silicon-based deposited film that can sufficiently satisfy the electrical and optical characteristics for each application, it is currently best formed by the plasma CVD method.

However, depending on the application of the silicon-based deposited film, it may be necessary to achieve a large area, film thickness uniformity, and film quality uniformity for mass production with reproducibility.
In forming a silicon-based deposited film by the VD method, a large amount of capital investment is required for mass production equipment, the management items for mass production are complicated, the control allowance is narrow, and the adjustment of equipment is delicate. From these, these are pointed out as problems to be improved in the future.

Further, in the case of the plasma CVD method, since plasma is directly generated by a high frequency wave or a microwave in the film formation space in which the substrate to be formed is arranged, electrons and a large number of ion species are generated. Causes damage to the film during the film formation process and causes deterioration of film quality and nonuniformity of film quality.

A method proposed as an improvement on this point is an indirect plasma CVD method.

In the indirect plasma CVD method, plasma is generated by microwaves or the like at an upstream position away from the film formation space, and the plasma is transported to the film formation space to selectively use chemical species effective for film formation. It is measured so that it can be done.

However, even in such a plasma CVD method, since transport of plasma is essential, the lifetime of the chemical species effective for film formation must be long, and naturally, the gas species used is limited,
Various deposited films cannot be obtained, a large amount of energy is required to generate plasma, and the generation and amount of chemical species effective for film formation are essentially not placed under simple control. The problem remains.

In contrast to the plasma CVD method, the photo CVD method is advantageous in that it does not generate ion species or electrons that damage the film quality and film quality, but there are not so many types of light sources, and the wavelength of the light source is large. Is also deviated to the ultraviolet region, a large light source and its power source are required for industrialization, and a window for introducing the light from the light source into the film formation space is covered during the film formation and the film is formed during film formation. There is a problem that the amount of light decreases, and in other words, the light from the light source does not enter the film formation space.

As described above, in the formation of the silicon-based deposited film, the points to be solved still remain, and energy saving can be achieved with a low-cost device while maintaining its practicable characteristics and uniformity. It is earnestly desired to develop a mass-production forming method. These can be mentioned as similar problems to be solved in other functional films such as a silicon nitride film, a silicon carbide film, and a silicon oxide film.

〔Purpose〕

An object of the present invention is to eliminate the above-mentioned drawbacks of the deposited film forming method, and at the same time provide a novel deposited film forming method which does not depend on the conventional forming method.

Another object of the present invention is to provide a deposited film forming method which can save energy and can easily control the film quality and can obtain a deposited film having uniform characteristics over a large area.

Still another object of the present invention is to provide a deposited film forming method which is excellent in productivity and mass productivity, and which can easily obtain a film having high quality and excellent physical properties such as electrical, optical and semiconductor properties. is there.

[Means for solving problems]

The deposited film forming method of the present invention to achieve the above object is a gas having the same properties as a gaseous raw material for forming a deposited film, and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material. At least one of the oxygen-based and nitrogen-based oxidizers is introduced into the reaction space and chemically contacted to generate a plurality of precursors including the precursor in the excited state. Among these precursors, at least one precursor is used as a supply source of the deposited film constituent to form a deposited film on the substrate in the film formation space.

[Action]

According to the above-described deposited film forming method of the present invention, energy saving as well as large area, film thickness uniformity, and film quality uniformity are sufficiently satisfied to simplify management and mass production, and to be used in a mass production apparatus. It does not require a large capital investment, the management items for its mass production are clarified, the management allowance range is wide, and the adjustment of the device is easy.

In the deposited film forming method of the present invention, the gaseous raw material used for forming the deposited film is subjected to an oxidative action by chemical contact with a gaseous oxidant. , The characteristics, the application, etc., and is appropriately selected as desired. In the present invention, the above-mentioned gaseous raw material and gaseous oxidant may be those which are made gaseous when they are chemically contacted, and in general, they are gas, liquid or solid. It doesn't matter.

When the raw material or oxidant for forming the deposited film is a liquid or a solid, a carrier gas such as Ar, He, N ₂ or H ₂ is used, and bubbling is performed while adding heat if necessary. A raw material for forming a deposited film and an oxidizing agent are introduced into the reaction space in a gaseous state.

At this time, the partial pressure and the 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 for forming the deposited film and the gaseous oxidizing agent.

As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral-based deposited film such as a semiconductor-based or electrically insulating silicon-based deposited film or a germanium-based deposited film is obtained, Linear and branched chain silane compounds, cyclic silane compounds, chain germanium compounds and the like can be mentioned as effective ones.

Specific examples of the linear silane compound Si _n H
_{2n + 2} (n = 1,2,3,4,5,6,7,8), as the branched chain silane compound, SiH ₃ SiH (Si
Examples of H ₃ ) SiH ₂ SiH ₃ and chain germane compounds include Ge _m H _{2m + 2} (m = 1,2,3,4,5). In addition to this, tin hydride such as SnH ₄ can be cited as an effective raw material if, for example, a deposited film of tin is formed.

Of course, these raw material substances may be used alone or in combination of two or more.

The oxidant used in the present invention is gaseous when introduced into the reaction space, and is effective only by chemical contact with a gaseous raw material for forming a deposited film which is simultaneously introduced into the reaction space. Oxygen-containing oxidants, nitrogen-based oxidizers, and halogen-based oxidizers can be given as specific examples of oxygen, such as air, oxygen, ozone, and N ₂ O.
₄ , N ₂ O ₃ , N ₂ O and other oxygen or nitrogen compounds,
Peroxides such as H ₂ O ₂ , F ₂ , Cl ₂ . Halogen gas such as Br ₂ and I ₂ and fluorine, chlorine and bromine in the nascent state can be cited as effective ones.

These oxidizers are gaseous and are introduced into the reaction space at a desired flow rate and supply pressure together with the gas of the raw material for forming the deposited film, introduced into the reaction space, and chemically collided with the raw material. The raw materials are brought into contact with each other and oxidized to efficiently generate a plurality of precursors including excited precursors.
The excited state precursors and other precursors that are produced serve as a source of constituents of the deposited film, at least one of which is formed.

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

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

In the present invention, the ratio of the introduction amount of the halogen-based oxidant and the oxygen-based and / or nitrogen-based oxidant into the reaction space is appropriately determined according to the type of the deposited film to be formed and desired characteristics. However, it is preferably 1000/1 to 1/50, more preferably 500/1 to 1/20, most preferably 100/1.
It is desirable to be set to about 1/10.

In the present invention, the deposited film forming process proceeds smoothly, a film having high quality and desired physical properties can be formed, and the combination with the kind of the raw material and the oxidizing agent as the film forming factor, The mixing ratio, the pressure at the time of mixing, the flow rate, the film forming space internal pressure, the gas flow pattern, and the film forming temperature (base temperature) are appropriately selected as desired. These film forming factors are organically related, and are not determined individually but are determined according to each other under mutual relation. In the present invention, the ratio of the amounts of the gaseous source material for forming a deposited film and the gaseous oxidant, which are introduced into the reaction space, is related to the film forming factors related to the above film forming factors. Although appropriately determined according to the desire, the introduction flow rate ratio is preferably 1/100 to 100/1, and more preferably 1/50 to 50/1.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to stochastically enhance the chemical contact between the gaseous raw material and the gaseous oxidant, but the reactivity is taken into consideration. Then, it is preferable to appropriately determine the optimum value as desired.
The pressure at the time of mixing is determined as described above, but the pressure at each introduction is preferably 1 × 10 ^−7.
Atmospheric pressure to 10 atmospheric pressure, more preferably 1 × 10 ⁻⁶ atmospheric pressure to 3 atmospheric pressure is desirable.

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 precursor (E) in the excited state generated in the reaction space and the precursor in some cases. The precursor (D) derived from the body (E) is appropriately set as desired so as to effectively contribute to the film forming process.

The internal pressure of the film formation space is, when the film formation space is openly continuous with the reaction space, the introduction pressure and the flow rate of the substrate-like raw material for forming the deposited film and the gaseous oxidant in the reaction space. In connection with the above, adjustment can be made by adding a device such as differential exhaust or using a large exhaust device.

Alternatively, when the conductance of the connecting portion between the reaction space and the film formation space is small, an appropriate exhaust device is provided in the film formation space,
The pressure in the film forming space can be adjusted by controlling the exhaust amount of the apparatus.

Further, when the reaction space and the film formation space are integrated and the reaction position and the film formation position are spatially different from each other, differential evacuation as described above or a large size with sufficient evacuation capacity is performed. It suffices if an exhaust device is provided.

The pressure in the film formation space as described above is determined in relation to the introduction pressure of the gaseous raw material substance and gaseous halogen oxidizing agent introduced into the reaction space, preferably 0.001 Tor
r to 100 Torr, more preferably 0.01 Torr to 30 Torr, most preferably 0.05 to 10 Torr.

Regarding the gas flow type, when the raw material for forming the deposited film and the oxidant are introduced into the reaction space, these are uniformly and efficiently mixed, and the precursor (E) is efficiently produced. Therefore, it is necessary to design in consideration of the geometrical arrangements of the gas inlet, the substrate and the gas outlet so that the film formation can be performed properly without any trouble. One suitable example of this geometric arrangement is shown in FIG.

The substrate temperature (Ts) at the time of film formation is individually set as desired according to the gas species used, the number of species of the deposited film to be formed and the required characteristics. In order to obtain, it is preferable that the temperature is from room temperature to 450 ° C, more preferably 50 to 400 ° C. In particular, when forming a silicon deposited film having better semiconductor properties and photoconductivity, the substrate temperature (Ts) is 70 to 350 ° C.
Is desirable. Further, when a polycrystalline film is obtained, the temperature is preferably 200 to 650 ° C., more preferably 30.
It is desirable that the temperature be 0 to 600 ° C.

As the ambient temperature (Tat) of the film formation space, the generated precursor (E) and the precursor (D) do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently generated. ) Is appropriately determined as desired in relation to the substrate temperature (Ts).

The substrate used in the present invention may be conductive or electrically insulating as long as it is appropriately selected according to the intended use of the deposited film to be formed. As the conductive substrate, for example, NiCr, stainless steel, Al, C
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pd and alloys thereof.

As the electrically insulating substrate, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics, paper and the like are usually used. It is preferable that at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is provided on the surface subjected to the conductive treatment.

For example, in the case of glass, the surface is NiCr, Al, C
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + S
nO ₂ ), a conductive film is provided by a thin film, or a synthetic resin film such as a polyester film is NiCr, Al, Ag, Pb, Zn, Ni, Au,
The surface is subjected to a conductive treatment by treatment with a metal such as Cr, Mo, Ir, Nb, Ta, V, Ti, Pt by vacuum vapor deposition, electron beam vapor deposition, sputtering, or the like, or by laminating with the metal. The shape of the support may be any shape such as a cylindrical shape, a belt shape and a plate shape, 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 film. Furthermore, if the difference in thermal expansion between the two is large, a large amount of strain may occur in the film, and a good quality film may not be obtained. Therefore, select and use a substrate with a close difference in thermal expansion between the two. Is preferred.

Further, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the generation of the conical structure, it is necessary to treat the surface of the substrate so that the film structure and the film structure can obtain desired characteristics. Is desirable.

FIG. 1 shows an example of an apparatus suitable for embodying 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.

A reaction space and a film formation space are provided in the apparatus body.

101 to 108 are cylinders filled with gas 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-108c are gas pressure gauges, 101d-108, respectively.
d and 101e to 108e are valves, and 101f to 1
Reference numerals 08f are pressure gauges showing the pressures inside the corresponding gas cylinders.

Reference numeral 120 denotes a vacuum chamber having a structure in which a gas introducing pipe is provided in an upper portion thereof, and a reaction space is formed in the downstream of the pipe, and the substrate 1 faces the gas outlet of the pipe.
It has a structure in which a film formation space in which the base holder 112 is provided so that 18 is installed is formed. The gas introduction pipe has a triple concentric circle arrangement structure, and the first gas introduction pipe 109 into which the gas from the gas cylinders 101 and 102 is introduced and the second gas from the gas cylinders 103 to 105 are introduced from the inside. Gas introduction pipe 110 and gas cylinder 1
It has a third gas introduction pipe 111 into which the gas from 06 to 108 is introduced.

For the gas discharge to the reaction space of each gas introduction pipe, it is designed such that the inner pipe is located farther from the surface position of the substrate. That is, the respective gas introduction pipes are arranged so that the outer pipes surround the inner pipes.

The supply of gas from the pipe cylinders to the respective introduction pipes is performed by gas supply pipelines 123 to 125, respectively.

Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 102 are evacuated by a vacuum exhaust device (not shown) via the main vacuum valve 119.

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

In the case of the present invention, the distance between the substrate and the gas outlet of the gas introduction pipe is in an appropriate state in consideration of the type of the deposited film to be formed, its desired characteristics, the gas flow rate, the internal pressure of the vacuum chamber, etc. However, it is preferably several mm
It is desirable that the length is 20 cm, more preferably 5 mm to 15 cm.

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

The substrate heater 113 is connected to the power source 115 via the conductor 114.
Is supplied with electric power.

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

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

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

The flow rate of the SiH ₄ gas filled in the cylinder 101 is 20
The F ₂ gas filled in the cylinder 103 is supplied from the gas introduction pipe 109 at a sccm of ₂ sccm at a flow rate of ₂ sccm.
From 0, the O ₂ gas filled in the cylinder 106 was introduced into the vacuum chamber 102 through the gas introduction pipe 111 at the flow rate of ₂ sccm and the He gas filled in the cylinder 108 at the flow rate of 40 sccm.

At this time, the pressure in the vacuum chamber 120 was adjusted to 100 mTorr by adjusting the opening / closing degree of the vacuum valve 119. Quartz glass (15 cm × 15 cm) was used as the substrate, and the distance between the gas inlet 111 and the substrate was set to 3 cm. SiH ₄
Pale white emission was strongly observed in the mixed region of gas, O ₂ gas, and F ₂ gas. The substrate temperature (Ts) was set between room temperature and 400 ° C. as shown in Table 1 for each sample.

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

Next, Table 2 shows the film thickness of each sample when the substrate temperature was fixed to 300 ° C. and the flow rate of SiH ₄ was changed.

At this time, the time for which the gas was flown was 3 hours for all the samples. Further, all the samples had an O ₂ gas flow rate of ₂ sccm and F ₂
The gas flow rate was 2 sccm, the He gas flow rate was 40 sccm, and the internal pressure was 100 mTorr.

Next, the substrate temperature is 300 ° C., the SiH ₄ gas flow rate is 20 sc
cm, O ₂ gas flow rate ₂ sccm, F ₂ gas flow rate ₂ sccc
Table 3 shows the film thickness values of the films of the respective samples obtained after flowing the respective gases for 3 hours while changing the He gas flow rate variously under the conditions of m, internal pressure 100 mTorr.

Next, the substrate temperature is 300 ° C., the SiH ₄ gas flow rate is 20 sc
cm, O ₂ gas flow rate ₂ sccm, F ₂ gas flow rate ₂ sccc
Table 4 shows the values of the film thickness of each sample prepared by changing the internal pressure to various values with m and He gas flow rates of 10 sccm.

The unevenness of the film thickness distribution of each sample shown in Tables 1 to 4 depended on the distance between the gas introducing pipe 111 and the substrate, the gas flow rates flowing through the gas introducing pipes 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 of the film thickness could be controlled within ± 5% in the substrate of 15 cm × 15 cm. This position almost always corresponded to the position of maximum emission intensity. In addition, it was confirmed from the electron diffraction results that the formed Si: O: H: F films were amorphous.

Also, a comb-shaped electrode (gap length 200 μm) of Al was vapor-deposited on the amorphous Si: O: H: F film of each sample to prepare a sample for conductivity measurement. Place each sample in a vacuum cryostat and apply a voltage of 100 V, and use a micro ammeter (YHP41
40B), the electric current was measured and the electric conductivity (σd) was tried to be obtained.
It was estimated to be ^-14 s / cm or less.

Example 2 Instead of introducing O ₂ gas in Example 1, N ₂ O ₄ gas was introduced from a 107 bomb to form a film (Sample 2).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm F _{2 2} sccm N ₂ O _{4 2} sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm Same as in Example 1, strong blue in the region where SiH ₄ gas and N ₂ O ₄ gas merge Light emission was observed. After blowing gas for 3 hours, about 6500Å A-Si: N: on the quartz glass substrate.
An O: H: F film was deposited.

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

After vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the A-Si: N: O: H: F film, the sample was placed in a vacuum cryostat, and dark conductivity (as in Example 1) σd) was measured but was below the measurement limit.

Example 3 Instead of introducing SiH ₄ gas in Example 1, 10
Si ₂ H ₆ gas was introduced from 2 cylinders to form a film (Sample 3).

The film forming conditions at this time are as follows.

Si ₂ H ₆ 20 sccm F _{2 2} sccm O ₂ 5 sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 After blowing gas for 3 hours, about 1.5 μm on the quartz glass base.
A-Si: O: H: F film was deposited.

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

A comb-shaped electrode of Al (gear length 200 μm) was vacuum-deposited on the A-Si: O: H: F film and then placed in a vacuum cryostat to measure the dark conductivity (σd). It was below the measurement limit.

Example 4 Instead of introducing SiH ₄ gas in Example 1, 10
GeH ₄ gas was introduced from 2 cylinders to form a film (Sample 4).

The film forming conditions at this time are as follows.

GeH ₄ 20 sccm F _{2 2} sccm O _{2 2} sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 After blowing gas for 3 hours, about 5500Å on the quartz glass substrate.
A-Ge: O: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

A comb-shaped electrode of Al (gear length 200 μm) was vacuum-deposited on the A-Ge: O: H: F film and then placed in a vacuum cryostat to measure dark conductivity (σd). Similarly, it was below the measurement limit.

Example 5 Introducing SiH ₄ gas in Example 1 and
GeH ₄ gas was introduced from 2 cylinders to form a film (Sample 5).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm GeH ₄ 5 sccm F _{2 3} sccm O ₂ 5 sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 hours after blowing gas for about 3800 Å on quartz glass substrate
A-SiGe: O: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the A-SiGe: O: H: F film, sample 5 was placed in a vacuum cryostat and the dark conductivity (σd) was measured. Like Example 1, it was below the measurement limit.

Example 6 Instead of introducing GeH ₄ gas in Example 5, 10
C ₂ H ₄ gas was introduced from 2 cylinders to form a film (Sample 6).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm C ₂ H ₄ 5 sccm F _{2 2} sccm O ₂ 5 sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 After gas blowing for 3 hours, about 6000 Å on quartz glass substrate
A-SiC: O: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing an Al-comb-shaped electrode (gear length of 200 μm) on the A-SiC: O: H: F film, sample 6 was placed in a vacuum cryostat and the dark conductivity (σd) was measured. Like Example 1, it was below the measurement limit.

Example 7 Introducing SiH ₄ gas in Example 1 and
Si ₂ H ₆ gas was introduced from 2 cylinders to form a film (Sample 7).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm Si ₂ H ₆ 5 sccm F ₂ 3 sccm O ₂ 5 sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 hours after blowing gas for about 3 μm on a quartz glass substrate
A-Si: O: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length of 200 μm) of Al on the A-Si: O: H: F film, sample 7 was placed in a vacuum cryostat and the dark conductivity (σd) was measured. Like Example 1, it was below the measurement limit.

Example 8 Instead of introducing O ₂ gas in Example 7, N ₂ O ₄ was introduced from the cylinder 107 to form a film (Sample 8).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm Si ₂ H ₆ 5 sccm F _{2 3} sccm N ₂ O ₄ 5 sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 hours After blowing gas for 3 hours, about 1.0 μ on a quartz glass substrate
m A-Si: N: O: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 μm) of Al on the A-Si: N: O: H: F film, the sample 8 was placed in a vacuum cryostat, and the dark conductivity (σd) was measured. However, it was below the measurement limit as in Example 1.

Example 9 Instead of introducing SiH ₄ gas in Example 1, 10
SnH ₄ gas was introduced from 2 cylinders to form a film (Sample 9).

The film forming conditions at this time are as follows.

SnH ₄ 10sccm F ₂ 5sccm O ₂ 20sccm He 40sccm Internal pressure 100mTorr Base temperature 300 ° C Distance between gas outlet and base 4cm After blowing gas for 3 hours, about 3000Å on quartz glass base
Sn: O: H: F film was deposited. When confirmed by electron beam diffraction, a diffraction peak was observed and it was found that this film was polycrystalline.

After vacuum-depositing a comb-shaped electrode of Al (gap length of 200 μm) on the poly-Sn: O: H: F film, Example 1 was performed.
In the same manner as in the above, the dark conductivity (σ
d) was measured respectively.

The obtained value was σd = 8 × 10 ⁻⁴ s / cm 2.

Example 10 The substrate temperature was set to 600 ° C. in Example 1 to form a film (Sample 10).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm F _{2 2} sccm O _{2 2} sccm He 40 sccm Internal pressure 100 mTorr Distance between gas outlet and substrate 3 cm 3 After blowing gas for 3 hours, about 500Å on quartz glass substrate
Si: O: H: F film was deposited. When this deposited film was confirmed by electron beam diffraction, a diffraction peak of SiO ₂ was observed,
It was found to be polycrystalline.

Sample 10 was formed by vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the poly-Si: O: H: F film.
Was placed in a vacuum cryostat and the dark conductivity (σd) was measured. As with Example 1, it was below the measurement limit.

Example 11 In Example 1, F ₂ gas was introduced and Cl ₂ gas was introduced from a 104 bomb to form a film (Sample 1).
1).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm F _{2 2} sccm Cl _{2 2} sccm O _{2 2} sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm Same as in Example 1, SiH ₄ gas, F ₂ , Cl ₂ gas and O ₂ gas A strong blue emission was observed in the area where the two merged.
After blowing gas for 3 hours, approximately 8000Å on the quartz glass substrate
A-Si: O: H: F: Cl film was deposited.

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

After vacuum-depositing an Al-comb-shaped electrode (gear length 200 μm) on the A-Si: O: H: F: Cl film, the sample was placed in a vacuum cryostat and dark conductivity (as in Example 1). σd) was measured but was below the measurement limit.

Example 12 Instead of introducing F ₂ gas in Example 1, Cl ₂ gas was introduced from a 104 bomb to form a film (Sample 1).
2).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm Cl _{2 2} sccm O _{2 2} sccm He 40 sccm Internal pressure 100 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm Same as in Example 1, S: iH ₄ gas and Cl ₂ gas and O ₂
A strong blue emission was observed in the area where the gas merges. After blowing gas for 3 hours, 3000 Å AS on the quartz glass substrate
An i: O: H: F: Cl film was deposited.

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

After vacuum-depositing an Al-comb-shaped electrode (gear length 200 μm) on the A-Si: O: H: F: Cl film, the sample was placed in a vacuum cryostat and dark conductivity (as in Example 1). σd) was measured but was below the measurement limit.

〔effect〕

From the above detailed description and each example, according to the deposited film forming method of the present invention, it is possible to obtain a deposited film having a uniform physical property over a large area while achieving energy saving and easy control of film quality. In addition, it has excellent productivity and mass productivity, high quality and electrical,
A film having excellent physical properties such as optical properties and semiconductor properties can be easily obtained.

[Brief description 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, 101a-108a ... Gas introduction pipe, 101b-108b ... Mass flow meter, 101c-108c ... Gas pressure gauge, 101d-108d and 101e-108e ... Valve, 101f-108f ... ... Pressure gauge, 109, 110, 111 ... Gas introduction pipe, 112 ... Substrate holder, 113 ... Substrate heating heater, 116 ... Substrate temperature monitoring thermocouple, 118 ... Substrate, 119 ... Vacuum exhaust valve , And, respectively.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 31/0248

Claims (16)

[Claims] 1. A gaseous source material for forming a deposited film, a gaseous halogen-based oxidizing agent having a property of oxidizing the source material, and gaseous oxygen-based and nitrogen-based oxidation having the same property. At least one of the agents is introduced into the reaction space and chemically contacted with each other to generate a plurality of precursors including excited state precursors, and at least one of the precursors is generated. A method for forming a deposited film, which comprises forming a deposited film on a substrate in a film forming space as a supply source of the deposited film constituent. 2. The method for forming a deposited film according to claim 1, wherein light is emitted 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 straight chain silane compound. 5. The linear silane compound has the general formula Si _n
The deposited film forming method according to claim 4, which is represented by H _{2n + 2} (n is an integer of 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 chain-like germane compound has the general formula Ge _m
The deposited film forming method according to claim 8, which is represented by H _{2m + 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 oxidant is an oxygen compound. 13. The deposited film forming method according to claim 1, wherein the gaseous oxidant is oxygen gas. 14. The deposited film forming method according to claim 1, wherein the gaseous oxidant is a nitrogen compound. 15. The deposition according to claim 1, wherein the substrate is arranged at a position facing the introduction direction of the gaseous raw material and the gaseous oxidant into the reaction space. Film formation method. 16. The method for forming a deposited film according to claim 1, wherein the gaseous raw material and the gaseous oxidant are introduced into the reaction space through a transport pipe having a multi-tubular structure.