JPH0647731B2 - 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 A-
It goes without saying that it falls into the category of Si (H, X))
Are formed by vacuum deposition, plasma CVD, thermal CVD.
Method, reactive sputtering method, ion plating method,
The optical 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 formal parameters of the deposited film (eg, basic temperature, flow rate and ratio of introduced gas, formation 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. The actual condition is that it is difficult to generalize the manufacturing conditions because it is necessary to select a parameter device unique to the device.

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

In addition, depending on the application of the silicon deposited film, it is necessary to achieve a large area, film thickness uniformity, and film quality uniformity to achieve reproducible mass production.
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, the transport of plasma is indispensable, so that the lifetime of the chemical species effective for film formation must be long, and naturally, the gas species used are limited, and various kinds of deposition are deposited. There are problems such as not being able to obtain a film, having a large amount of energy to generate plasma, and being essentially unable to place the generation and amount of chemical species effective for film formation under simple control. It 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, a large light source and its power source are required for industrialization, and the window for introducing the light from the light source into the film formation space is coated during film formation, so the amount of light during film formation There is a problem that the light from the light source is not incident on the film formation space.

As described above, there are still problems to be solved in the formation of the silicon deposited film, and it is possible to mass-produce by saving energy with a low-cost device while maintaining its practicable characteristics and uniformity. It is highly desired to develop a 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 to provide a novel deposited film forming method that does not rely on the conventional forming method.

Another object of the present invention is to provide a deposited film forming method capable of achieving energy saving and at the same time easy control of film quality and obtaining a deposited film having a uniform property 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 substrate-like raw material for forming a deposited film and a substrate-like halogen-based oxidizing agent having a property of oxidizing the raw material are introduced into a reaction space. And chemically contact with each other, thereby causing a chemical reaction accompanied by light emission to generate a plurality of precursors including a precursor in an active state, and a region having an emission intensity of ⅕ or less of the maximum intensity of the emission. And depositing the deposited film on the substrate by using at least one of the precursors as a supply source of the deposited film constituent.

According to the above-described deposition forming method of the present invention, energy saving as well as large area, film thickness uniformity, and film quality uniformity can be sufficiently satisfied to simplify management and mass production, and to achieve a large mass production apparatus. No capital investment is required, the management items for mass production are clarified, the management allowance is wide, and the adjustment of the device is easy.

[Specific Description of the Invention]

In the deposited film forming method of the present invention, the substrate-like raw material used for forming the deposited film is one that undergoes an oxidizing action by chemical contact with a gaseous halogen-based oxidizing agent, and It is appropriately selected depending on the type, characteristics, application, etc., as desired. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidant may be those that are brought into a gaseous state at the time of chemical contact, and in the usual case, they are gas, liquid or solid. It does not matter if there is.

When the principle substance for deposition formation or the halogen-based oxidizer is liquid or solid, use a carrier gas such as Ar, He, H ₂ , H ₂ and perform bubbling while adding heat if necessary. As a result, the raw material for forming the deposited film and the halogen-based oxidizing agent can be 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. Examples of effective compounds include linear and branched chain silane compounds, cyclic silane compounds, and chain germanium compounds.

Specifically, as a linear silane compound, Si _n H _{2n + 2} (n
= 1,2,3,4,5,6,7,8), a branched chain silane compound is SiH ₃ SiH (SiH ₃ ) SiH ₂ SiH ₃ , and a chain germane compound is Ge _m H _{2m. +2} (m = 1, 2, 3, 4, 5) and the like can be mentioned.
In addition, SnH ₄
And the like can be cited as an effective raw material.

Of course, these raw materials may be used alone or in admixture 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,
_{F 2, Cl 2, Br 2} , I 2, FCl, halogen gas such as FBr, fluorine nascent state, chlorine, can be mentioned bromine as valid.

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,
Alternatively, a deposited film having a three-dimensional network structure is formed by releasing energy as needed but touching the surface of the substrate arranged in the film-forming space in its original form.

The excited energy level causes the precursor of the excited state to undergo energy transition to a lower energy level,
Or, the energy level accompanied by light emission is included in the process of changing 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 deposited film formation of the present invention, strong chemiluminescence is observed in a certain region including the position where the gaseous raw material and the gaseous halogen-based oxidant are mixed. A region exhibiting light emission with an intensity of 1/5 or more of the maximum intensity of this light emission is referred to as a light emitting region (A), and a region other than the light emitting region (A) is referred to as a non-light emitting region (B). The size and shape of the light emitting region (A) vary depending on the flow rate of the gaseous raw material, the flow rate of the gaseous halogen-based oxidant, the internal pressure of the film forming space, the internal size and internal shape of the apparatus, and the like. It was confirmed that this luminescence was mainly based on SiF ^* when, for example, a material containing Si was used as a raw material and a material containing F was used as a halogen-based oxidizing agent.

In the present invention, the non-light emitting region (B) in the film forming space
Since the substrate is placed in the
-The basic temperature is 80 to 23 in the film formation of Si (H, X).
A relatively high deposition rate of 10 even at a low temperature of 0 ° C.
˜50 Å / sec is obtained, and the physical properties of the film are good despite the high speed film formation. By the way,
When the substrate is arranged in the light emitting region (A) in the film forming space,
Even under similar conditions, a relatively low deposition rate of 1-2 Å / sec can be obtained.

In the present invention, the deposited film forming process proceeds smoothly, a film having high quality and desired physical properties can be formed, and as a film forming factor, in combination with the kinds of the raw material and the halogen-based oxidizing agent, 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 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 source material for forming the deposited film and the gaseous halogen-based oxidant introduced into the reaction space is related to the film forming factor related to the vapor film forming factor. It can be appropriately determined according to the desire, but it is preferably the introduction flow rate ratio,
1/20 to 20/1 is suitable, and more preferably 1 /
It is preferably set to 5 to 5/1.

The pressure at the time of mixing when introduced into the reaction space is higher than the higher method in order to establish the chemical contact between the gaseous raw material and the gaseous halogen-containing oxidant in a definite manner. 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 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 gas for forming a film on the surface thereof 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 gaseous source 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. And in relation to the flow rate, for example, working exhaust or use of a large exhaust device or the like can be added and adjusted.

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 damage device.

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, either the operation exhaust gas as described above or a large-sized exhaust gas having a sufficient exhaust capacity is provided. An exhaust device may be provided. As described above, the pressure of the film forming space is determined in relation to the introduction pressure of the gaseous raw material substance and the gaseous halogen oxidizing agent introduced into the reaction space, but preferably 0.001 Torr to 100 Torr, more preferably Is 0.01 Torr to 30 Torr, optimally 0.05 to 1
It is desirable to set it to 0 Torr.

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 formed properly 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 set as appropriate according to the gas species used, the type of deposited film to be formed and the required characteristics, and an amorphous film is obtained. In this case, it is preferably room temperature to 450 ° C., more preferably 5
The temperature is preferably 0 to 400 ° C. In particular, when forming a silicon deposited film having better semiconductor properties and photoconductivity, the basic temperature (Ts) is preferably 70 to 350 ° C. When obtaining a polycrystalline film, it is preferably 200 to 650 ° C, more preferably 300 to 60 ° C.
It is preferably set to 0 ° 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 basic 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, Cr, Mo, A
Metals such as u, Ir, Nb, Ta, V, Ti, Pt, and Pb, or alloys thereof can be used.

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 or polyamide, glass, ceramic or the like is 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, Cr, Mo,
Au, Ir, Nb, Ta, V, Ti, Pt, Pb, In ₂ O ₃ , SnO ₂ , ITO (In
₂ O ₃ + SnO ₂ ), etc. are applied to make conductive,
Or synthetic resin film such as polyester film, NiCr, Al, Ag, Pd, Zn, Ni, Au, Cr, Mo, Ir, N
A metal such as b, Ta, V, Ti, or Pt is vacuum-deposited, electron-beam-deposited, sputtered, or laminated, or is laminated with the metal, and its surface is subjected to a conductive treatment. The shape of the support may be any shape such as a cylindrical shape, a belt shape, 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, since a large amount of strain may occur in the film having a large difference in thermal expansion between the two and a good quality film may not be obtained, it is recommended to select and use a substrate having a close difference in thermal expansion between the two. preferable.

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 have a desired property. Is desirable.

FIG. 1 is a schematic view showing 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 gas flow rates from the cylinders, respectively.
01c-108c are gas pressure gauges, 101d-1
08d and 101e to 108e are valves and 101f, respectively.
˜108f are pressure gauges showing the pressures inside the corresponding gas cylinders.

Reference numeral 120 denotes a vacuum chamber having a structure in which a pipe for introducing gas is provided in the upper part and a reaction space is formed in the downstream of the pipe, and facing the gas outlet of the pipe, the substrate 1
It has a structure in which a film formation space in which the substrate holder 112 is arranged is formed so that 18 is arranged. The gas introducing pipe has a triple concentric arrangement structure, and the first gas introducing pipe 109 into which the gas from the gas cylinders 101 and 102 is introduced, and the second gas into which the gas from the gas cylinders 103 to 105 is introduced. Introduction pipe 110 and gas cylinder 106-
Third gas introduction pipe 111 into which gas from 108 is introduced
Have.

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.

Gas is supplied from the gas cylinders to the respective introduction pipes by gas supply pipelines 123 to 125, respectively.

Each gas introduction pipe, each gas supply pipeline, and the inside of the vacuum chamber 120 are vacuum-exhausted by a vacuum exhaust device (not shown) through the main vacuum valve 119.

The substrate 118 can be installed at an appropriate desired distance of the position of each gas introduction pipe by moving the substrate holder 112 up and down.

In the present invention, the distance between the substrate 118 and the gas outlet of the gas introduction pipe is appropriately determined in consideration of the type of deposited film to be formed, desired characteristics thereof, gas flow rate, internal pressure of the vacuum chamber 120, and the like. However, preferably several mm to 20 m
m, more preferably about 5 mm to 15 cm.

Reference numeral 113 denotes a substrate heater which is used to heat the substrate 118 to an appropriate temperature during film formation, to preheat the substrate 118 before film formation, and to heat the film to anneal after film formation. Is. The base heater 113
Is supplied with power from a power supply 115 via a conductor 114.

Reference numeral 116 is a thermocouple for measuring 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 apparatus shown in FIG. 1, a deposited film was formed by the method of the present invention as follows.

Flow rate of SiH ₄ gas filled in the cylinder 101 is 100sc
The flow rate of the F ₂ gas diluted to 10% with the He gas filling the cylinder 106 is 1000 sc from the gas introduction pipe 109 at a flow rate of 1000 sc.
From the gas inlet pipe 111 in cm, vacuum chamber 1
It was introduced in 20. At this time, the opening / closing degree of the vacuum valve 119 is adjusted to adjust the pressure in the vacuum chamber 120 to 400 mTo.
I set it to rr.

A strong blue emission was observed in the mixed region of SiH ₄ and F ₂ gas.

FIG. 2 is a diagram showing this light emission state.

In FIG. 2, A is a light emitting region and B and B'are non-light emitting regions. When the emission intensity at each position on the line III in FIG. 2 was focused using a fiber lens and detected by a photodiode array, the emission intensity distribution as shown in FIG. 3 was obtained. Also in FIG. 3, A indicates a light emitting region, and B and B ′ indicate non-light emitting regions. In FIG. 3, the position is measured from the mixing start position of the raw material gas and the halogen-based oxidant gas, that is, from the lower end of the gas introduction pipe 109, and the quartz glass substrate (10 cm × 10 cm) is used for this measurement. ) Was placed 10 cm from the lower end of the gas introduction pipe 109.

The temperature (Ts) of the quartz glass substrate (10 cm x 10 cm) is set to 2
A deposited film was formed for 10 minutes each under the same conditions as in the case of measuring the emission intensity described above except that the temperature was set to 00 ° C. and the distance from the gas mixing start position of the substrate was changed.
A Si: H: F film having a film thickness as shown in Table 1 was deposited on the substrate. The unevenness of the film pressure distribution of the deposited film on the substrate arranged in the non-light emitting region B was within ± 0.5% in all the samples. The formed Si: H: F film was It was confirmed by electron diffraction that the sample was also 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. Each sample was placed in a vacuum cryostat and a voltage of 100 V was applied to the microcurrent system (YHP4140).
The current was measured in B) to determine the dark conductivity (σd). Again 6
Nm, it is irradiated with light of 0.3 mW / cm ^2, photoconductivity (sigma
p) was determined. The results are shown in Table 1. The table also shows the measurement results of the ratio of the emission intensity (I) at the film forming position of the substrate to the maximum emission intensity (Imax) when the sample was prepared.

Next, the position of the substrate was fixed to 5 cm from the gas mixing start position tube (lower end position of 109), and the flow rate of the SiH ₄ gas was variously changed to form a deposited film. In addition, F ₂ gas diluted to 5% with He gas was introduced into the vacuum chamber 120 at a flow rate of 1000 sccm. In addition, the pressure in the vacuum chamber 120 is set to 4
The substrate temperature was 220 ° C.

Table 2 shows the film thickness of each sample and the locations of σd and σp at this time. In addition, I / Imax at the time of making each sample is 1/5
It was below. Further, the film forming rate was 15 to 40 Å / sec.

Next, the substrate temperature is set to 200 ° C. and the SiH ₄ gas flow rate is set to 20 sc
cm, the pressure in the vacuum chamber is 300 mTorr,
The flow rate of F ₂ gas diluted to 5% with He gas was changed to form a deposited film for 30 minutes. The substrate was positioned 5 cm from the gas mixing start position.

Table 3 shows the values of the samples σd and σp at this time. The I / Imax at the time of making each sample was 1/5 or less. The film forming rate was 15 to 40 Å / sec.

Next, the substrate temperature is set to 200 ° C. and the SiH ₄ gas flow rate is set to 20 sc
cm and set the flow rate of F ₂ gas diluted to 5% with He gas to 1000
As sccm, change the pressure in the vacuum chamber to 3
The deposited film was formed for 0 minutes. The substrate was positioned 5 cm from the gas mixing start position.

Table 4 shows the values of σd and σp of the film of each sample at this time.
The I / Imax at the time of making each sample was 1/5 or less. The film forming rate was 15 to 40 Å / sec.

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 rate flowing through the gas introducing pipes 109 and 111, and the internal pressure of the vacuum chamber 120.

In addition, the formed Si: H: F films of all samples were
According to the result of electron diffraction, it was confirmed to be amorphous.

Example 2 In Example 1, the cylinder 107 was further filled.
Cl ₂ gas diluted to 5% with He gas was introduced into the gas introducing pipe 111.
Further, it was introduced into the vacuum chamber 120 to form a deposited film (Sample 2).

The film forming conditions at this time were as follows.

SiH ₂ 20sccm F ₂ / He 500sccm Cl ₂ / He 500sccm Internal pressure 350mTorr Basic temperature 200 ° C Distance between gas outlet and basic 5cm Same as in Example 1, from the position where SiH ₄ gas and (F ₂ + Cl ₂ ) gas meet A strong blue luminescence with a maximum intensity was observed at a position of about 2 cm. After introducing the gas for 30 minutes, a space of about 3 μm of A—Si: H: F: Cl 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 (gap 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 band gap (Eg ^opt ) was measured by measuring the conductivity (σp) at the time of light irradiation with m and 0.3 mw / cm ² , and the optical absorption.

The obtained value was σd = 2 × 10 ⁻¹¹ s / cm σp = 9 × 10 ⁻⁷ s / cm Eg ^opt = 1.65 eV.

For comparison, in the sample in which the basic position is 1.5 cm and the deposited film is formed in the light emitting region (A), the film thickness is 0.8 μm σd = 5 × 10 ⁻¹¹ s / cm σp = 7 × 10 ^-7 s / cm Eg ^opt = 1.6 eV.

Example 3 Instead of introducing SiH ₄ gas in Example 1, Si ₂ H ₆ gas was introduced from the cylinder 103 to form a film (Sample 3).

The film forming conditions at this time were as follows.

Si ₂ H ₆ 20 sccm F ₂ / He (5% F ₂ ) 1000 sccm Internal pressure 300 mTorr Basic temperature 200 ℃ Distance between gas outlet and basic 5 cm Si ₂ H ₆ and F ₂ gas are located about 3 cm from the confluence. Strong blue emission with maximum intensity was observed. After introducing the gas for 10 minutes, about 1.7 μm AS on the quartz glass substrate.
An i: 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 (gap length 200 μm) on the A-Si: H: F film, the sample was placed in a vacuum cryostat, and the dark conductivity (σd), 600 nm, 0.3 nm.
The conductivity (σp) at the time of light irradiation of mw / cm ² was measured.

The obtained value was σd = 6 × 10 ^-11 s / cm σp = 3 × 10 ^-6 s / cm.

For comparison, in the sample in which the position of the substrate is 1.5 cm and the deposited film is formed in the light emitting region (A), the film pressure is 0.5 μm σd = 3 × 10 ⁻¹¹ s / cm σp = 9 × 10 It was ^-6 s / cm.

Example 4 Instead of introducing SiH ₄ gas in Example 1, GeH ₄ gas was introduced from the cylinder 104 to form a film (Sample 4).

The film forming conditions at this time were as follows.

GeH ₄ 20sccm F ₂ / He (10% F ₂ ) 1000sccm Internal pressure 300mTorr Substrate temperature 200 ℃ Distance between gas outlet and basic 5cm At this time, the maximum strength is about 2cm from the confluence of GeH ₄ gas and F ₂ gas. Strong blue light emission was observed. After introducing gas for 20 minutes, about 1.6 μm of A− was formed on the quartz glass substrate.
A Ge: 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 (gap length 200 μm) on the A-Ge: H: F film, the sample was placed in a vacuum cryostat, and the dark conductivity (σd), 600 nm, 0.
The electrical conductivity (σp) when irradiated with light of 3 mw / cm ² was measured.

The obtained value was σd = 6 × 10 ⁻⁷ s / cm σp = 5 × 10 ⁻⁶ s / cm.

Example 5 In Example 1, SiH ₄ gas was introduced, and GeH ₄ gas was introduced from the cylinder 104 to form a film. (Sample 5).

The film forming conditions at this time were as follows.

SiH ₄ 20sccm GeH ₄ 5sccm F ₂ / He (5% F ₂ ) 1200sccm Internal pressure 400mTorr Substrate temperature 200 ℃ Distance between gas outlet and basic 5cm At this time, maximum strength is about 2cm from the outlet of the gas outlet pipe. Blue light emission was observed. After introducing gas for 20 minutes, about 1.9 μm A-SiG was formed on the quartz glass substrate.
An e: H: F film was deposited. It was confirmed to be amorphous by electron beam diffraction.

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

The obtained value σd = 8 × 10 ^-9 s / cm σp = 6 × 10 ^-6 s / cm.

Example 6 Instead of introducing GeH ₄ gas in Example 5, C ₂ H ₄ gas was introduced from the cylinder 105 to form a film (Sample 6).

The film forming conditions at this time were as follows.

SiH ₄ 20sccm C ₂ H ₄ 5sccm F ₂ 1200sccm Internal pressure 400mTorr Substrate temperature 200 ° C Distance between gas outlet and basic 5cm After introducing gas for 30 minutes, about 1.1μ on 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 an Al-comb-shaped electrode (gap length 200 μm) on the A-SiC: H: F film, a sample 6 was placed in a vacuum cryostat, and the dark conductivity (σd), 600 nm,
The optical band gap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) at the time of irradiation with light of 0.3 mw / cm ² and the optical absorption.

The obtained value was σd = 6 × 10 ⁻¹³ s / cm σp = 3 × 10 ⁻⁸ s / cm Eg ^opt = 1.9 eV.

For comparison, in the sample in which the basic position is 1.5 cm and the deposited film is formed in the light emitting region (A), the film pressure is 0.4 μm σd = 8 × 10 ⁻¹¹ s / cm σp = 2 × 10 ^-8 s / cm Eg ^opt = 1.85 eV.

Example 7 In Example 1, SiH ₄ gas was introduced and Si ₂ H ₆ gas was introduced from the cylinder 103 to form a film (Sample 7).

The film forming conditions at this time were as follows.

SiH ₄ 20sccm S ₂ H ₆ 5sccm F ₂ / He (10% F ₂ ) 1200sccm Internal pressure 400mTorr Substrate temperature 200 ℃ Distance between gas outlet and base 5cm At this time, maximum strength is about 2cm from the gas outlet A strong blue light was seen. After introducing the gas for 10 minutes, about 1.3 μm of A-Si: H: on the quartz glass substrate.
F film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing a comb-shaped electrode of Al (gap length 20 μm) on the A-Si: H: F film, a sample 7 was placed in a vacuum cryostat, and the dark conductivity (σd), 600 nm, 0.
The optical band gap (Eg ^opt ) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of ³ mw / cm ² and the optical absorption.

The obtained value was σd = 6 × 10 ⁻¹¹ s / cm σp = 1 × 10 ⁻⁶ s / cm Eg ^opt = 1.65 eV.

Example 8 In Example 7, F ₂ gas was introduced and Cl ₂ gas was introduced from the cylinder 107 to form a film (Sample 8).

The film forming conditions at this time were as follows.

SiH ₄ 20sccm Si ₂ H ₆ 5sccm F ₂ / He (10% F ₂ ) 800sccm Cl ₂ / He (10% Cl ₂ ) 400sccm Internal pressure 400mTorr Basic temperature 200 ℃ Distance between gas outlet and basic 5cm A strong blue luminescence with a maximum intensity was observed at a position about 1 cm from the confluence. After introducing the gas for 10 minutes, about 1.9 μm of A-Si: H: on the quartz glass base.
An F: Cl film was deposited. It was confirmed by electron diffraction that the film was amorphous.

After vacuum-depositing a comb-shaped electrode of Al (gap length 200 μm) on the A-Si: H: F: Cl film, the sample 8 was placed in a vacuum cryostat, and the dark conductivity (σd), 600.
The optical bandgap (Eg ^opt ) from the measurement of optical conductivity (σp) and optical absorption at wavelength of 0.3 mw / cm ²
Was measured.

The obtained value was σd = 6 × 10 ⁻¹¹ s / cm σp = 8 × 10 ⁻⁷ s / cm Eg ^opt = 1.70 eV.

Example 9 In Example 1, the basic temperature was set to 600 ° C. to form a film (Sample 8).

The film forming conditions at this time were as follows.

SiH ₄ 20 sccm F ₂ / He (5% F ₂ ) 1000 sccm Internal pressure 450 mTorr Distance between gas outlet and basic 5 cm Similar to Example 1, about 2 cm from the confluence of SiH ₄ gas and F ₂ gas
A strong blue luminescence with maximum intensity was observed at the position. Three
After introducing gas for 0 minutes, approximately 1.2 μm on the quartz glass base
Si: H: F film was deposited. When the deposited film was measured by electron diffraction, a diffraction peak of Si was observed and it was found that the film was polycrystallized.

A comb-shaped electrode of Al (gap length 2
(9 μm) was vacuum-deposited, and then Sample 9 was placed in a vacuum cryostat, and the optical bandgap (Eg ^opt ) was measured by measuring dark conductivity (σd) and optical absorption.

The obtained value was σd = 6 × 10 ⁻³ s / cm Eg ^opt = 1.9 eV.

Example 10 In Example 1, SiH ₄ gas was introduced, and SnH ₄ gas was introduced from the cylinder 102 to form a film (Sample 1).
0).

The film forming conditions at this time were as follows.

SiH ₄ 20sccm SnH ₄ 5sccm F ₂ / He (5% F ₂ ) 1200sccm Inner pressure 350mTorr Basic temperature 230 ℃ Distance between gas outlet and basic 5cm Strong with maximum strength at a position about 2cm from the outlet of the gas outlet pipe Blue light emission was observed. After introducing gas for 20 minutes, about 1.9 μm of A-SiS was formed on the quartz glass base.
An n: H: F film was deposited. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode of Al (gap length 200 μm) on the A-SiSn: H: F film, the sample 10 was placed in a vacuum cryostat, and the dark conductivity (σd), 600.
The electrical conductivity (σp) at the time of irradiation with light having a wavelength of 0.3 mw / cm ² was measured.

The value obtained was σd = 2 × 10 ⁻⁸ s / cm σp = 1 × 10 ⁻⁷ s / cm.

〔The invention's effect〕

As can be seen from the above detailed description and the description of each example, according to the deposited film forming method of the present invention, energy saving can be achieved and at the same time, the film quality can be easily controlled. Furthermore, it is possible to obtain a functional deposited film having uniform properties over a large area.

In addition, it has excellent productivity, mass productivity, high quality, electrical,
A film having excellent physical properties such as optical properties and semiconductor properties can be easily obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a deposited film forming apparatus used in an example of the present invention. FIG. 2 is a diagram showing a state of light emission in the embodiment of the method of the present invention, and FIG. 3 is a graph showing an intensity distribution of the light emission. 101-108 ... Gas cylinder, 109-111 ... Gas introduction pipe, 112 ... Substrate holder, 113 ... Substrate heating heater, 116 ... Substrate temperature monitoring thermocouple, 118 ... Substrate, 119 ... Vacuum exhaust Valve, 120 ... Vacuum chamber, A ... Luminescent region, B, B '... Non-luminous region.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 21/205 31/04

Claims (17)

[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 chemically contacted with each other. To generate a plurality of precursors including a precursor in an active state by causing a chemical reaction accompanied by luminescence, and positioning the substrate in a region having a luminescence intensity of ⅕ or less of the maximum luminescence intensity. A method for forming a deposited film, comprising forming a deposited film on the substrate by using at least one precursor of the above as a supply source of the deposited film constituent. 2. The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain silane compound. 3. The deposited film forming method according to claim 2, wherein the chain silane compound is a straight chain silane compound. 4. The linear silane compound has the general formula Si _n H.
The deposition film forming method according to claim 3, wherein the deposition film is represented by _{2n + 2} (n is an integer of 1 to 8). 5. The deposited film forming method according to claim 2, wherein the chain silane compound is a branched chain silane compound. 6. The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure. 7. The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound. 8. The chain germane compound has the general formula Ge _m H
The deposited film forming method according to claim 7, which is represented by _{2m + 2} (m is an integer of 1 to 5). 9. The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound. 10. The deposited film forming method according to claim 1, wherein the gaseous source material is a tetrahedral compound. 11. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains a halogen gas. 12. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains fluorine gas. 13. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas. 14. The gaseous halogen-based oxidizing agent is a gas containing a fluorine atom as a constituent.
The method for forming a deposited film according to item. 15. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state. 16. The method according to claim 1, wherein the substrate is arranged at a position opposed to a direction in which the gaseous source material and the gaseous halogen-based oxidizing agent are introduced into the reaction space. Method for forming deposited film. 17. 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.