JPH0645882B2 - 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 for forming a silicon deposited film by the plasma CVD method, which has been generalized in the past, is considerably complicated as compared with the conventional CVD method, and the reaction mechanism has few unclear points. Absent. 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 deposited film capable of sufficiently satisfying 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 deposited film, it is necessary to achieve a large area, film thickness uniformity, and film quality uniformity for mass production with reproducibility.
In forming a silicon deposited film by the D method, a large amount of capital investment is required for a mass production device, the management items for the mass production are complicated, the control allowance is narrow, and the adjustment of the device is delicate. However, 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 film quality and film quality, but there are not so many kinds of light sources, and the wavelength of the light source Is also deviated to the ultraviolet region, a large light source and its power source are required in the case of industrialization, and the window for introducing the light from the light source into the film formation space is covered during film formation and is being formed. In addition, there is a problem that the light amount is reduced, and in the worst case, the light from the light source is not incident on the film formation space.

As described above, there are still points to be solved in the formation of the silicon deposited film, and while maintaining the practicable characteristics and uniformity, it is possible to mass-produce by saving energy with a low-cost device. It is eagerly desired to develop a forming method capable of forming. 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]

In the deposited film forming method of the present invention which achieves the above object, a gaseous raw material for forming a deposited film and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material are introduced into a reaction space. Then, a precursor in an excited state is generated by the chemical contact, and the precursor is used as a supply source of the deposited film constituent to form the 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 halogen-based oxidant, and the desired deposited film is obtained. It is appropriately selected according to the desired type, characteristics, application, etc. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidizing agent may be those that are made gaseous when they are chemically contacted, and in the usual case, they are gas, liquid or solid. But it doesn't matter.

When the raw material for forming the deposited film or the halogen-based oxidant 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 as necessary. As a result, the raw material for forming the deposited film and the halogen-based oxidizing agent are introduced into the reaction space in a gaseous state.

At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidant are 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 oxidant. Is set.

As the raw material for forming the deposited film used in the present invention, for example, a linear chain deposited film such as a semiconductor or electrically insulating silicon deposited film or a germanium deposited film may be used in order to obtain a linear film. A chain-like or branched chain-like silane compound, a cyclic silane compound, a chain-like germanium compound 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 halogen-based oxidant used in the present invention is gasified when introduced into the reaction space, and at the same time, only by chemical contact with a gaseous raw material for forming a deposited film which is introduced into the reaction space. It has the property of effectively oxidizing, and F
Halogen gas such as ₂ , Cl ₂ , Br ₂ and I ₂ , nascent fluorine, chlorine, bromine and the like can be cited as effective ones.

These halogen-based oxidants 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, and are mixed and collided with the raw material. The precursor is chemically contacted with the raw material to oxidize the raw material to efficiently generate a plurality of precursors including a precursor in an excited state. 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 in 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 deposited film forming process proceeds smoothly, and a film having high quality and desired physical properties can be formed. The combination, the mixing ratio of these, the pressure at the time of mixing, the flow rate, the internal pressure of the film forming space, the gas flow type, and the film forming temperature (base temperature and atmospheric 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 raw material substance for forming a deposited film and the gaseous halogen-based oxidant introduced into the reaction space is related to the film forming factors related to the above film forming factors. In this case, the introduction flow rate ratio is preferably set to 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 halogen-based oxidant, but the reactivity is higher. Considering the above, 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 the time of introducing each is preferably 1 × 10 ⁻⁷ atm to 10 atm, more preferably 1 × 10 ⁻⁶ atm to 3 atm. It is desirable to be done.

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 film formation.

The internal pressure of the film formation space is the pressure introduced into the reaction space between the base material for forming a deposited film and the gaseous halogen-based oxidant when the film formation space is open and continuous with the reaction space. In relation to the flow rate and the flow rate, it is possible to make adjustments by adding, for example, 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.

As described above, the pressure in the film forming space is determined by the relationship between the gaseous source material introduced into the reaction space and the introduction pressure of the gaseous halogen oxidant, and preferably 0.001 T
orr to 100 Torr, more preferably 0.01 Torr
-30 Torr, optimally 0.05-10 Torr is desirable.

Regarding the gas flow type, when the raw material for forming the deposited film and the halogen-based oxidant are introduced into the reaction space, these are uniformly and efficiently mixed, and the precursor (E) is efficiently mixed. It is necessary to design in consideration of the geometrical arrangement of the gas inlet, the substrate and the gas outlet so that the film can be properly formed and the film can be properly formed. 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 either 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.

The gas introduction pipes, the gas supply pipelines, and the vacuum chamber 120 are vacuum-exhausted 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 106 was introduced into the vacuum chamber 102 through the gas introduction pipe 111 through the gas introduction pipe 109 at a flow rate of ₂ sccm and the He gas filled in the cylinder 107 at a flow rate of 40 sccm.

At this time, the pressure in the vacuum chamber 120 was adjusted to 800 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 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 the gas was flown for 3 hours in this state, a Si: H: F film having a film thickness as shown in Table 1 was deposited on the substrate.

The unevenness of the film thickness distribution was within ± 5%. It was confirmed by electron beam diffraction that all the formed Si: H: F films were amorphous.

A comb-shaped electrode (gap length 200 μm) of Al was vapor-deposited on the amorphous Si: 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 (YHP4140).
The current was measured in B) to determine the dark conductivity (σd). Again 6
The photoconductivity (σp) was obtained by irradiating with light of 00 nm, 0.3 mw / cm ² . Further, the optical bandgap (Eg ^opt ) was determined from the absorption of light. The results are shown in Table 1.

Next, the substrate temperature was fixed at 300 ° C., and the film thickness of each sample was prepared by varying the flow rate of SiH ₄ , σd, σp, Eg
The results of ^opt are shown in Table 2.

At this time, the time for which the gas was flown was 3 hours for all the samples. In addition, all the samples were F ₂ gas flow rate ₂ sccm, He
The gas flow rate was 40 sccm and the internal pressure was 800 mTorr.

Next, the substrate temperature is 300 ° C., the SiH ₄ gas flow rate is 20 sc
cm, F ₂ gas flow rate ₂ sccm, inner thickness 800 mTorr
And the film thickness of each sample obtained after flowing each gas for 3 hours with various He gas flow rates changed, σd, σp, Eg
Table 3 shows the values of ^opt .

Next, the substrate temperature is 300 ° C., the SiH ₄ gas flow rate is 20 sc
cm, F ₂ gas flow rate ₂ sccm, He gas flow rate 40 sc
Table 4 shows the film thickness, σd, σp, and Eg ^opt of the film of each sample prepared by changing the internal pressure to various values.

The unevenness of the film thickness distribution of each sample shown in Tables 1 to 4 depended on the distance between the gas introduction pipe 111 and the substrate, the gas flow rate flowing through the gas introduction pipes 109 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, the deposited S
It was confirmed that the i: H: F films of all samples were amorphous according to the result of electron beam diffraction.

Example 2 A film was formed by introducing F ₂ gas and Cl ₂ gas from a 107 cylinder in Example 1 (Sample 2).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm F _{2 2} sccm Cl _{2 2} sccm He 40 sccm Internal pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm Similar to Example 1, strong blue in a region where SiH ₄ gas and (F ₂ + Cl ₂ ) gas merge. Light emission was observed. After blowing out the gas for 3 hours, about 2.5 μm AS on the quartz glass substrate
An i: 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: H: F: Cl film, the sample was placed in a vacuum cryostat, and the dark conductivity (σd), 600 n.
The optical bandgap (Eg ^opt ) is obtained by measuring the electrical conductivity (σp) at the time of irradiation with light of m, 0.3 mw / cm ² and optical absorption.
Were measured respectively.

The obtained value was σd = 4 × 10 ⁻¹¹ s / cm σp = 8 × 10 ⁻⁷ s / cm Eg ^opt = 1.70 eV.

Example 3 Instead of introducing SiH ₄ gas in Example 1, 10
Si ₂ H ₆ gas was introduced from 3 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 5 sccm He 40 sccm Internal pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm 3 Strong blue emission was observed in the region where Si ₂ H ₆ gas and F ₂ gas merged. After blowing out the gas for 1 hour, an A-Si: H: F film of about 1.8 μm was deposited on the quartz glass substrate.

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: H: F film, it was placed in a vacuum cryostat, dark conductivity (σd), 600 nm, 0.3 mw /
The optical bandgap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of cm ² and the optical absorption.

The obtained value was σd = 8 × 10 ⁻¹¹ s / cm σp = 2 × 10 ⁻⁶ s / cm Eg ^opt = 1.70 eV.

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

The film forming conditions at this time are as follows.

GeH ₄ 20 sccm F ₂ 4 sccm He 40 sccm Inner pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm At this time, intense blue emission was observed at the confluence of GeH ₄ gas and F ₂ gas. After the gas was blown for 2 hours, an A-Ge: H: F film of about 1.5 μm was deposited on the quartz glass substrate. 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-Ge: H: F film, the film was placed in a vacuum cryostat, dark conductivity (σd), 600 nm, 0.3 mw.
The optical bandgap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of / cm ² and the optical absorption.

The obtained value was σd = 8 × 10 ⁻⁷ s / cm σp = 3 × 10 ⁻⁶ s / cm Eg ^opt = 1.0 eV.

Example 5 Introducing SiH ₄ gas in Example 1 and
GeH ₄ gas was introduced from 4 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 5 sccm He 40 sccm Internal pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm At this time, strong blue light emission was observed near the outlet of the gas outlet tube. After blowing out the gas for 2 hours, an A-SiGe: H: F film of about 2.0 μm was deposited on the quartz glass substrate. It was confirmed to be amorphous by electron beam diffraction.

After vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the A-SiGe: H: F film, a sample 5 was placed in a vacuum cryostat, and the dark conductivity (σd), 600 n.
The optical bandgap (E) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of m, 0.3 mw / cm ² and optical absorption.
g ^opt ) was measured respectively.

The obtained value was σd = 3 × 10 ⁻⁹ s / cm σp = 1 × 10 ⁻⁷ s / cm Eg ^opt = 1.4 eV.

Example 6 Instead of introducing GeH ₄ gas in Example 5, 10
C ₂ H ₄ gas was introduced from 5 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 5 sccm He 40 sccm Internal pressure 800 mTorr Substrate temperature 300 ° C. Distance between gas outlet and substrate 3 cm After blowing gas for 3 hours, about 1.0 μ on the quartz glass substrate
m of A-SiC: 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-SiC: H: F film, sample 6 was placed in a vacuum cryostat, and the dark conductivity (σd), 600 n.
The optical bandgap (E) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of m, 0.3 mw / cm ² and optical absorption.
g ^opt ) was measured respectively.

The obtained value was σd = 8 × 10 ⁻¹³ s / cm σp = 1 × 10 ⁻⁸ s / cm Eg ^opt = 1.9 eV.

Example 7 Introducing SiH ₄ gas in Example 1 and
Si ₂ H ₆ gas was introduced from 3 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 5 sccm He 40 sccm Inner pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm At this time, strong blue light emission was observed near the gas outlet. After blowing out the gas for 1 hour, about 1
A 1.2 μm A-Si: 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: H: F film, a sample 7 was placed in a vacuum cryostat, and dark conductivity (σd), 600 nm,
The optical bandgap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) when irradiated with light of 0.3 mw / cm ² and the optical absorption.

The obtained value was σd = 7 × 10 ⁻¹¹ s / cm σp = 9 × 10 ⁻⁷ s / cm Eg ^opt = 1.65 eV.

Example 8 In Example 7, F ₂ gas was introduced and Cl ₂ 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 Cl _{2 2} sccm He 40 sccm Inner pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm When gas was flowed, strong blue emission was observed at the confluence of gas. After blowing out the gas for 1 hour, about 1
A 1.8 μm A-Si: H: F: Cl 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: H: F: Cl film, the sample 8 was placed in a vacuum cryostat, and the dark conductivity (σd), 600
nm, conductivity (σp) when irradiated with light of 0.3 mw / cm ² ,
And optical bandgap (Eg
^opt ) was measured.

The obtained value was σd = 8 × 10 ⁻¹¹ s / cm σp = 9 × 10 ⁻⁷ s / cm Eg ^opt = 1.70 eV.

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 10} sccm F ₂ 20 sccm He 40 sccm Internal pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 4 cm At this time, light emission was observed at the confluence of SnH ₄ gas and F ₂ gas. After blowing out the gas for 3 hours, approximately 3 hours on the quartz glass substrate.
A 1.0 μm Sn: H: F film was deposited. When confirmed by electron beam diffraction, it was found that this film was amorphous.

After vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the A—Sn: H: F film, the electrode was placed in a vacuum cryostat as in Example 1, and the dark conductivity (σd) and optical absorption The optical bandgap (Eg ^opt ) was measured from the measurement.

The obtained value was σd = 3 × 10 ⁻⁶ s / cm Eg ^opt = 0.80 eV.

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 He 40 sccm Internal pressure 800 mTorr Distance between gas outlet and substrate 3 cm Similar to Example 1, strong blue emission was observed at the confluence of SiH ₄ gas and F ₂ gas. After blowing out the gas for 3 hours, a Si: H: F film of about 1.0 μm was deposited on the quartz glass substrate. When the deposited film was confirmed by electron beam diffraction, a diffraction peak of Si was observed and it was found that the film was polycrystallized.

On the Si: H: F film, a comb-shaped electrode of Al (gear length 2
(10 μm) was vacuum-deposited and then the sample 10 was placed in a vacuum cryostat, and the optical bandgap (Eg ^opt ) was measured by measuring the dark conductivity (σd) and the optical absorption.

The obtained value was σd = 3 × 10 ⁻³ s / cm Eg ^opt = 1.4 eV.

Example 11 Introducing SiH ₄ gas in Example 1 and
SnH ₄ gas was introduced from a 4-cylinder to form a film (Sample 11).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm SnH ₄ 5 sccm F _{2 3} sccm He 40 sccm Internal pressure 800 mTorr Base temperature 300 ° C. Distance between gas outlet and base 3 cm At this time, strong blue light emission was observed near the outlet of the gas outlet tube. After the gas was blown for 2 hours, an A-SiSn: H: F film of about 2.2 μm was deposited on the quartz glass substrate. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 μm) of Al on the A-SiSn: H: F film, the sample 11 was placed in a vacuum cryostat, and the dark conductivity (σd), 600
nm, conductivity (σp) when irradiated with light of 0.3 mw / cm ² ,
And optical bandgap (Eg
^opt ) was measured respectively.

The obtained value was σd = 3 × 10 ⁻⁸ s / cm σp = 9 × 10 ⁻⁸ s / cm Eg ^opt = 1.2 eV.

Example 12 Instead of SiH ₄ gas in Example 1, Al ₂ (CH
₃ ) A cylinder filled with ₆ gas was connected to a connecting port of a 102 gas cylinder, and Al ₂ (CH ₃ ) ₆ was bubbled with He gas to flow to form a film (Sample 12). The bubbling temperature was 60 ° C. He gas cylinder is cylinder 101
And 106.

The film forming conditions at this time are as follows.

He flow rate when Al ₂ (CH ₃ ) was bubbled 20 sccm F ₂ 5 sccm He flow rate together with F ₂ gas 40 sccm Inner pressure 800 mTorr Base temperature chamber Base temperature of quartz base gas outlet and base 3 cm Light emission was observed from the vicinity of the outlet of the air outlet to the substrate.

After blowing out the gas for 30 minutes, a 3000 Å Al film was deposited on the quartz substrate. The conductivity was almost the same as that of Al prepared by vacuum evaporation. The adhesion to the quartz substrate was remarkably better than that of the vacuum-deposited Al film.

Example 13 In Example 1, W (CO) ₆ was used instead of SiH ₄ gas.
The cylinder was a 102 gas cylinder. And W (CO) ₆
Was bubbled and flowed with He gas to form a film (Sample 13). The bubbling temperature was 60 ° C. The He gas cylinders were two cylinders 101 and 106.

The film forming conditions at this time are as follows.

He flow rate when W (CO) ₆ was bubbled 20 sccm F ₂ 5 sccm He flow rate together with F ₂ gas 40 sccm Internal pressure 800 mTorr Base temperature chamber Base temperature quartz base Gas outlet and base distance 3 cm Gas outlet at this time Light emission was observed from the vicinity of the exit of the substrate to the substrate.

After blowing out the gas for 30 minutes, a W film of 5000 Å was deposited on the quartz substrate. The conductivity was almost the same as that of the W film formed by electron beam vacuum evaporation. The adhesion to the quartz substrate was significantly better than that of the Al film obtained by electron beam evaporation.

Example 14 Instead of flowing SiH ₄ gas in Example 1, H ₂ Se was used.
A gas was passed to form a film (Sample 14).

The film forming conditions at this time are as follows.

H ₂ Se 20 sccm F _{2 10} sccm He 40 sccm Internal pressure 800 mTorr Substrate temperature 60 ° C. Substrate Quartz substrate Distance between gas outlet and substrate 3 cm When gas was flowed, light emission was observed from the vicinity of the outlet of the gas outlet tube to the substrate.

After blowing out the gas for 30 minutes, about 2 μm S on the quartz substrate.
e film was deposited.

As a result of electron beam diffraction, it was confirmed that the obtained Se film was amorphous. A comb-shaped Al electrode was deposited on the Se film by a vacuum deposition method, and the dark conductivity (σ
The optical bandgap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) at the time of irradiation with light of d), 600 nm, and 0.3 mw / cm ² .

The obtained value was σd = 3 × 10 ⁻¹³ s / cm σp = 2 × 10 ⁻⁸ s / cm Eg ^opt = 2.1 eV.

Example 15 Instead of introducing F ₂ in Example 1, Cl ₂ gas was introduced from a 107 cylinder to form a film (Sample 1).
5).

The film forming conditions at this time are as follows.

SiH ₄ 20 sccm Cl _{2 2} sccm He 40 sccm Internal pressure 800 mTorr Substrate temperature 300 ° C. Distance between gas outlet and substrate 3 cm At this time, strong emission was observed at the point where SiH ₄ gas and Cl ₂ gas merge. After blowing out the gas for 3 hours, an A-Si: H: Cl film of about 1.5 μm was deposited on the quartz glass substrate. 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: H: Cl film, a sample 15 was placed in a vacuum cryostat, and the dark conductivity (σd), 600 n.
The optical bandgap (E) was measured by measuring the electrical conductivity (σp) at the time of irradiation with m, 0.3 mw / cm ²
g ^opt ) was measured.

The obtained value was σd = 2 × 10 ^-11 s / cm σp = 6 × 10 ^-8 s / cm Eg ^opt = 1.70 eV.

〔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 the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // G03G 5/08 105 9223-2H

Claims (18)

[Claims] 1. A gaseous raw material for forming a deposited film and a gaseous halogen-based oxidizer having a property of oxidizing the raw material are introduced into a reaction space and brought into chemical contact with each other. Producing a plurality of precursors, including excited state precursors, and forming a deposited film on a substrate within a deposition space with at least one of these precursors as a source of deposited film components. A method for forming a deposited film, characterized by: 2. The method for forming a deposited film according to claim 1, wherein light is emitted during generation. 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 halogen-based oxidizing agent contains a halogen gas. 13. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains fluorine gas. 14. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas. 15. The gas-based halogen-based oxidizing agent is a gas containing a fluorine atom as a constituent.
The method for forming a deposited film according to item. 16. The method for forming a deposited film according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state. 17. The substrate according to claim 1, wherein the substrate is arranged at a position opposed to the introduction direction of the gaseous raw material and the gaseous halogen-based oxidant into the reaction space. Method for forming deposited film. 18. The method for forming a deposited film according to claim 1, wherein the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space through a transport pipe having a multi-tubular structure.