JPS6296675A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To easily obtain a uniform deposited film having high quality by forming a deposited film on a substrate with a precursor produced from a gaseous starting material and a gaseous oxidizing agent contg. halogen as a source for feeding a film forming element so as to simplify the control of the quality of a film. CONSTITUTION:A gaseous starting material (a chain silane compound) and a gaseous oxidizing agent contg. halogen and having oxidizing action on the starting material are introduced into a reaction space, where they are brought into chemical contact with each other to produce plural kinds of precursors including an excited precursor. A deposited film is formed on a substrate with one or more kinds of such precursors as sources for feeding a deposited film forming element.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to functional films, particularly electronic devices such as semiconductor devices, photosensitive devices for electrophotography, and pre-input sensor devices for optical image input devices. The present invention relates to a method for forming a functional deposited film useful for applications.

[Conventional technology]

Conventionally, amorphous or polycrystalline functional films such as semiconductor films, insulating films, photoconductive films, magnetic films, or metal films have been formed by forming films that are individually suited from the viewpoint of desired physical properties and applications. method has been adopted.

For example, if necessary, amorphous or polycrystalline non-single crystal silicon (rNON-5t (H,
X) J is abbreviated as rA-S i (H,
For the formation of silicon deposited films such as H, , vacuum method,
Plasma CVD methods, thermal CVD methods, 9 reactive sputtering methods, ion blating methods, optical CVD methods, and the like have been tried, and in general, plasma CVD methods are widely used and commercialized.

[Problem that the invention seeks to solve]

However, the reaction process in forming silicon salt JAM by the conventionally popular plasma CVD method is as follows.
It is considerably more complicated than the conventional CVD method, and its reaction mechanism has many unknown points, and there are many parameters for forming the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, formation time, etc.). Due to the combination of these many parameters (pressure, high-frequency power, electrode structure, structure of the reaction vessel, pumping speed, plasma generation method, etc.), the plasma can sometimes become unstable and have a significant negative impact on the deposited film formed. It was not uncommon to give Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions.

On the other hand, in order to develop a silicon deposited film that satisfies the electrical and optical characteristics for each application, it is currently considered best to form it by plasma CVD.

However, depending on the application of the silicon deposited film, it is necessary to increase the area, uniformity of the film thickness, etc. II! 2.In forming silicon deposited films by plasma CVD method, it is necessary to fully satisfy the uniformity of quality and achieve mass production with reproducibility.
Mass production equipment requires a large capital investment, the management items for mass production are complicated, the management tolerance is narrow, and equipment adjustments are delicate, so these are issues that need to be improved in the future. This is pointed out as a point.

In addition, in the case of the plasma CVD method, since plasma is directly generated by high frequency waves or microwaves in the film forming space where the substrate to be filmed is placed, electrons and many ion species are generated. This causes damage to the film during the film formation process, causing deterioration of film quality and non-uniformity of film quality.

One indirect plasma CVD method has been proposed as an improvement on this point.

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

However, since the plasma CVD method also requires plasma transport, the lifetime of the chemical species effective for film formation must be extended, which naturally limits the types of gases that can be used.
These problems include the inability to obtain various deposited films, the need for a large amount of energy to generate plasma, and the fact that the production and amount of chemical species effective for film formation cannot be easily controlled. The problems are stacked.

The photo CVD method is different from the plasma CVD method.

Although it is advantageous in that it does not generate ion species or electrons that can damage H and H during film formation, it is difficult to industrialize because there are not so many types of light sources, and the wavelength of the light source is biased toward the ultraviolet. In some cases, a large light source and its power source are required, and the window that introduces the light from the light source into the deposition space is covered with a film during deposition, resulting in a decrease in light intensity during deposition, and in some cases, the light from the light source decreases. There is a problem that the film is no longer incident on the film forming space.

As mentioned above, there are still many issues to be solved regarding the formation of silicon deposited films.

There is a strong desire to develop a forming method that can be mass-produced using low-cost equipment and energy saving while maintaining its practically usable characteristics and uniformity. These can be applied to other functional films, such as silicon nitride films, silicon carbide films,
Similar problems to be solved can also be raised for silicon oxide films.

〔the purpose〕

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

Another object of the present invention is to provide a method for forming a deposited film that saves energy, allows easy control of film quality, and provides a deposited film with uniform characteristics over a large area.
)ei6゜: Yet another object of the present invention is to
Another object of the present invention is to provide a method for forming a deposited film that is excellent in productivity and mass production, and can easily produce a film of high quality and excellent physical properties such as electrical, optical, and semiconductor properties.

[Means for solving problems]

The deposited film forming method of the present invention which achieves the above object introduces into a reaction space a gaseous raw material for the deposited film forming method and a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material. The method is characterized in that a precursor in an excited state is generated by chemically contacting the deposited film, and the precursor is used as a source of a deposited film component to form a deposited film on a substrate located in a deposition space. .

[Effect]

According to the deposited film forming method of the present invention described above, it is possible to save energy, increase the area, uniformity of film thickness, and uniformity of film quality, simplify management and mass production, and save a lot of money on mass production equipment. It does not require major capital investment, the control items for mass production become clear, the control tolerance is wide, and equipment adjustment becomes easy.

In the deposited film forming method of the present invention, the gaseous raw material used for forming the deposited film is oxidized by chemical contact with the gaseous halogen-based M-forming agent. Type of membrane.

They are appropriately selected depending on characteristics, uses, etc. as desired. In the wood F6 light, the above-mentioned gaseous raw material and gaseous halogen-based oxidizing agent may be any material as long as it is in a gaseous state upon chemical contact.

In normal cases, it may be gas, liquid, or solid.

When the raw material for forming the deposited film or the halogen-based oxidizing agent is liquid or solid, Ar.

He, N2. ) (Using a carrier gas such as No. 2, bubbling is performed while adding heat if necessary, and a raw material for forming a deposited film and a halogen-based oxidizing agent are introduced in gaseous form into the reaction space.

At this time, the partial pressure and mixing ratio of the gaseous raw material and the gaseous halogen-based oxidizing agent can be adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous halogen-based oxidizing agent. Set.

As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral deposited film such as a semiconducting or electrically insulating silicon deposited film or germanium deposited film is to be obtained, it can be directly used. Effective examples include chain and branched chain silane compounds, IM disilane compounds, and chain germanium compounds.

Specifically, the linear silane compound is SinH2n.
+2 (n=1,2,3,4,5゜6.7.8),
As the branched chain silane compound, S 1H3S i
H(SiH3)S 1H2s iH3, as a chain germane compound, Gem82m+2 (m=1.2, 3.
4.5) etc. In addition, for example, if a deposited film of tin is to be created, tin hydride such as SnH4 can be used as an effective raw material.

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

The halogen-based oxidizing agent used in the present invention is in a gaseous state when introduced into the reaction space, and is simultaneously introduced into the reaction space through chemical contact with the gaseous raw material for forming a deposited film. It has the property of effectively oxidizing, and F
2°C12, Br2. Effective examples include halogen gas such as I2, nascent fluorine, chlorine, and bromine.

These halogen-based oxidizing agents are in a gaseous state, and are introduced into the reaction space together with the gas of the raw material material for forming the deposited film, given a supply pressure of the desired Ef, -1i, and mixed with the raw material material indicated by if. The collision causes chemical contact and oxidizes the raw material to efficiently generate a plurality of types of precursors including excited Y-island precursors. The excited state precursors and other precursors that are generated serve as a source of components for the deposited film in which at least one of them is formed.

The precursors produced can be decomposed or reacted to become a precursor in an excited state or a precursor in another excited state, or they can remain in their original form, though they release energy as needed. A deposited film having a three-dimensional network structure is created by touching the surface of the substrate disposed in the film-forming space.

The excited energy level is preferably an energy level that accompanies luminescence in the process of energy transition of the excited state precursor to a lower energy level or change into another chemical species, such as 1IJT energy. The deposited film forming process of the present invention proceeds more efficiently and with less energy by forming activated precursors including excited state precursors that are accompanied by light emission during the transition of As a result, a deposited film that is uniform and has better physical properties is formed.

In the present invention, the type and type of raw material and halogen-based oxidizing agent are selected as film-forming factors so that the deposited film forming process can proceed smoothly and a film with high quality and desired physical properties can be formed. The combination, their mixing ratio, the pressure during mixing, the flow rate, the internal pressure of the film forming space, the waveform of the gas, and the film forming temperature (substrate temperature and ambient temperature) are appropriately selected as desired.

These film formation factors are organically related and are not determined independently, but are determined according to each other in mutual relationship.
In the present invention, the ratio of the amounts of the gaseous raw material for forming a deposited film and the gaseous halogen-based oxidizing agent introduced into the reaction space is determined based on the relationship between the film-forming factors and the intermediate speed of the above-mentioned film-forming factors. Although it can be determined as desired, the introduction flow rate ratio is preferably 1/100 to 100/1, more preferably 1150 to 50/1.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to increase the probability of chemical contact between the gaseous raw material and the gaseous halogen-based oxidizing agent. It is preferable to determine the optimum value as desired by considering the following.

The pressure at the time of mixing is determined as described above, but the pressure at the time of each introduction is preferably lXl0-
7 atm to 10 atm, more preferably IXIQ-6 atm to
It is desirable that the pressure be 3 atm.

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

When the film forming space is open and continuous with the reaction space, the internal pressure of the film forming space is the pressure introduced into the reaction space between the substrate-like raw material for forming the deposited film and the gaseous halogen oxidant. In relation to the flow rate, it is possible to adjust the flow rate by, for example, using a differential exhaust system or a large exhaust system.

Alternatively, if the fundductance of the connection between the reaction space and the film-forming space is small, an exhaust device that communicates with the film-forming space may be provided, and the pressure in the film-forming space may be adjusted by controlling the exhaust volume of the device. You can.

In addition, if the reaction space and film-forming space are integrated and only one reaction position and film-forming position are spatially different, use differential pumping as described above, or use a large-scale pump with sufficient exhaust capacity. It is best to install an exhaust system.

As described above, the pressure in the film forming space is determined based on the relationship between the gaseous raw material introduced into the reaction space and the introduction pressure of the gaseous halogen oxidizing agent, and is preferably 0.00.
1Torr ~ lOOTorr, more preferably 0.0ITorr ~ 30Torr, optimally 0.05
It is desirable to set it to 10 Torr.

Regarding the original form of the gas, when the raw material for forming conjunctival membranes and the halogen-based oxidizing agent are introduced into the reaction space, they are mixed uniformly and efficiently, and the precursor (E) is efficiently mixed. The geometrical arrangement of the gas inlet, the substrate, and the gas outlet must be designed in consideration of the geometric arrangement of the gas inlet, the substrate, and the gas outlet so that the gas can be generated and the film can be formed properly without any problems. One preferred example of this geometry is shown in FIG.

The substrate temperature (Ts) during film formation is set as desired depending on the type of gas used, the number of types of deposited film to be formed, and the required characteristics. The temperature is preferably from room temperature to 450°C, more preferably from 50 to 400°C, especially when forming a silicon deposited film with better properties such as semiconductivity and photoconductivity. The substrate temperature (Ts) is desirably 70 to 350°C, and in the case of obtaining a polycrystalline film, it is preferably 200 to 650°C, more preferably 300°C.
It is desirable that the temperature be 600°C.

The atmospheric temperature (Tat) in the film-forming space is set such that the precursor (E) and the precursor (D) that are produced do not change into inappropriate chemical species during the formation process, and that the precursor (Tat) is efficiently E)
It is determined as desired in relation to the substrate temperature (TS) so that TS is generated.

The substrate used in the present invention may be electrically conductive or electrically insulating, as long as it is selected as desired depending on the use of the deposited film to be formed. 1 For example.

NiCr, Steer L/S, An, Cr, Mo, Au,
Examples include gold scraps such as Ir, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof.

Electrically insulating substrates include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, and polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NiCr.

An, Cr, Mo, Au, Ir, Nb, Ta, V, T
i, Pt, Pd, In2O3,5n02, ITO(I
NiCr, An, Ag, Pb, if it is conductive treated by providing a thin film such as n203+5n02) or a synthetic resin film such as polyester film.
Zn, Ni, Au, Cr, Mo, Ir, Nb, T
The surface is treated with a metal such as a, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, or the like, or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined according to desire.

It is preferable to select the substrate from among 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 distortion will occur in the film, making it difficult to obtain a good quality film. Therefore, it is preferable to select and use a substrate whose thermal expansion difference is close to that of the two substrates.

In addition, the surface condition of the substrate is directly related to the structure (orientation) of the film and the occurrence of cone-shaped structures, so it is important to treat the surface of the substrate so that it has a film structure and structure that provides the desired properties. is desirable.

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

The deposited film forming apparatus shown in FIG. 1 is a main body of the apparatus.

It is roughly divided into three parts: exhaust system and gas supply system.

The main body of the apparatus is provided with one reaction chamber and a film forming space.

101-108 are cylinders filled with gases used for film formation, 101a-108a are gas supply pipes, 101b-108b are Tumas flow controllers for adjusting the flow rate of gas from each cylinder, 101
c to 108c are gas pressure gauges, 101d to 108, respectively.
d and 101e-108e are valves, 1otf to 1, respectively.
08f is a pressure gauge that indicates the pressure inside the corresponding gas cylinder.

Reference numeral 120 denotes a vacuum chamber, which has a structure in which a pipe for introducing gas is provided at the upper part and a reaction space is formed downstream of the pipe.
It has a structure in which a film forming space is formed in which a substrate holder 112 is provided so that the substrate holder 1B is installed. The piping for gas introduction has a triple concentric arrangement structure, and a first gas introduction pipe 109. into which gas from the gas cylinder lot 102 is introduced from inside. A second gas introduction pipe 110 into which gas from the gas cylinders 103 to 105 is introduced, and the gas cylinder 1
It has a third gas introduction pipe 111 into which gases from 06 to 108 are introduced.

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

Gas is supplied from a tube cylinder to each inlet tube.

are provided by gas supply pipelines 123-125, respectively.

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

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

In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is determined appropriately by taking into consideration the type of deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. It can be determined as desired, but preferably several mm to 2
It is desirable that the length be 0 cm, more preferably about 5 mm to 15 cm.

Reference numeral 113 denotes a substrate heater that heats the substrate 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the film for 7 anneals after film formation. It is.

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

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

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

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

The SiH4 gas filled in the cylinder lot has a flow rate of 20
secm, the F2 gas filled in the port/vessel 106 is introduced into the vacuum chamber 102 through the gas introduction pipe 109 at a flow rate of 2 sccm, and the He gas filled in the port/veneer 107 is introduced into the vacuum chamber 102 through the gas introduction pipe 111 at a flow rate of 40 sccm. did.

At this time, the pressure inside the vacuum chamber 120 was adjusted to 800 mTorr by adjusting the opening/closing degree of the vacuum valve 119. The base was made of quartz glass (15 cm x 15 cm), and the distance between the gas inlet 111 and the base was set to 3 cm. SiH4
A strong blue-white luminescence was observed in the mixed region of gas and F2 gas.

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

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

Furthermore, the unevenness in film thickness distribution was within ±5%.

It was confirmed by electron diffraction that all of the Si:H:F films formed were amorphous.

Amorphous Si:H:Fil' of each sample! An A-shaped comb-shaped electrode (gap length 200 JLm) was deposited thereon to prepare a sample for conductivity measurement. Each sample was placed in a vacuum taliostat, a voltage of 100V was applied, and a microcurrent meter (YHP41
40B), and the dark conductivity (σd) was determined.

Further, 600 nm and 0.3 mw/cm2 light was irradiated to determine the photoconductivity (σP). Furthermore, the optical band gap (EgOPt) was determined from light absorption. These results are shown in Table 1.

Table 1 Next, the film thickness, σd, σp,
The results of E gopt are shown in Table 2.

At this time, the gas was flowed for 3 hours for all samples. In addition, for each sample, the F2 gas flow rate was sec, the He gas flow was 40 s cm, and the internal pressure was 800 mTo.
It was set as rr.

Table 2 Next, the substrate temperature was set to 300°C, and the SiH4 gas flow rate was set to 20se.
cm, F2 gas flow i2sccm, inner thickness 800mTorr
The film thickness, σd, σp of each sample obtained after flowing each gas for 3 hours with various He gas flows.
, Egopt values are shown in Table 3.

Table 3 Next, the substrate temperature was set to 300°C, and the 5tH4 gas flow rate was set to 20SC.
Cm, F2 gas flow rate 2 sccm, He gas flow rate 4
Table 4 shows the film thickness, σd, σP, and E-tube t values of each sample prepared by varying the internal pressure at 0 sec.

Table 4 The uneven distribution of film thickness of each sample shown in Tables 1 to 4 depended on the distance between the gas introduction tube ill and the substrate, the gas flow rate flowing through the gas introduction tubes 109 and 111, and the internal pressure. By adjusting the distance between the gas inlet pipe and the substrate in each of the six samples, the uneven distribution of film thickness could be kept within ±5% on a substrate measuring 15 cm x 15 cm. This position corresponded in most cases to the position of maximum emission intensity. Also, the S
According to the results of electron beam diffraction, it was confirmed that the i:H:F films of all samples were amorphous.

Example 2 In Example 1, F2 gas was introduced and Cu2 gas was also introduced from the 107 cylinder to form a film (Sample 2).
.

The film forming conditions at this time are as follows.

5i) i4 20secF2
2 sc Cm(,4122sc
cm He 40sec Internal pressure
800mTorr substrate temperature
300℃□: Distance between gas outlet and base 3
cm□: Same as Example 1, SiH4 gas and (F2
+, C1z) fj't#r<h flow t″' region 1°゛“Pyroluminescence” was observed, after 3 hours of gas blowing 1 quartz was deposited on the lath substrate with approximately 2.5 gm of A-Si: H:F
:0 A film was deposited.

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

: After vacuum-depositing an A-shaped comb-shaped electrode (gap length 200 lm) on the A-St:H:F:C film, the sample was placed in a vacuum thalazeostat, and the dark conductivity (σ
d), electrical conductivity (σp) upon irradiation with light of 600 nm, 0.3 mw 70 m2, and optical band gap (E gOPt) were measured by measuring optical absorption.

The value obtained is σd = 4X 10-11s/. .

σp=8X10-7s/. .

EgOPt=1.70eV Met.

Example 3 Instead of introducing SiH4 gas in Example 1, 10
A film was formed by introducing Si 2H6 gas from No. 3 cylinder (Sample 3).

The film forming conditions at this time are as follows.

Si2H620sec F2 5 s c cmHe
40sccm internal pressure
800mTo r rsubstrate temperature
Distance between 300℃ gas outlet and base: 3cm5t
Intense blue light emission was observed in the region where 2H6 gas and F2 gas merge. After one hour of gas blowing, about 1.8 pm of an A-Si+H:F film was deposited on the 6-piece glass substrate.

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

After vacuum-depositing a comb-shaped electrode (gap length 200 m) on the A-5i:H:F film, it was placed in a vacuum cryostat, and the dark conductivity (CRD) was 600 nm, 0.3.
The electrical conductivity (σp) upon irradiation with light of mw/cm 2 and the optical band gap (EgOpt) were measured by measuring optical absorption.

The value obtained is crd==8X10-Its/cm crp=2X l 0-Gs/cm EgOPt = 1.70eV Met.

Example 4 Instead of introducing 5iHa gas in Example 1, 10
GeH4 gas was introduced from the 4 cylinder to form a film (
Sample 4).

The film forming conditions at this time are as follows.

G e H420S CCm F2 4sccm) (640sc
cm Internal pressure 800mTo r r Base temperature
The distance between the 300°C gas outlet and the substrate was 3 cm.At this time, strong blue light was observed at the confluence of GeH4 gas and F2 gas. After blowing out gas for 2 hours,
Approximately 1.5 gm of A-Ge:H:F film was deposited on the fused silica substrate. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing an A-shaped comb-shaped electrode (gap length 200 ILm) on the A-Ge:H:F film, it was placed in a vacuum cryostat and the dark conductivity (CRD) was 600 nm, 0.
The optical band gap (E g 'Pt
) were measured respectively.

The value obtained is σd=8X10-7s/. engineering σp=3X104s/. .

Eg Oρ'=1. OeV Met.

Example 5 In addition to introducing SiH4 gas in Example 1,
GeH4 gas was introduced from the 04 pump to form a film (Sample 5).

The film forming conditions at this time are as follows.

SiH420secm GeH4,5secm F2 5secm He 40secm Internal pressure 800mTorr Substrate temperature 300°C Distance between gas outlet and substrate 3cm At this time, strong blue light emission was observed near the outlet of the gas outlet tube.

After 2 hours of gas blowing, approximately 2.0
7Lm A-5iGe:H:Fff! I was deposited. It was confirmed by electron beam diffraction that it was amorphous.

After vacuum-depositing an A-shaped electrode (gap length 200 ILm) on the A-3iGe:H:F film, sample 5 was placed in a vacuum cryostat, and the dark conductivity (CRD) was measured.
The electrical conductivity (σp) upon irradiation with light of 600 nm and 0.3 mw/cm 2 and the optical band gap (Eg'Pt) were measured by measuring optical absorption.

The obtained values were crd = 3X 10-9s/cm σp = IXlo-7s/Cm EgOPj = 1.4eV Example 6 Instead of introducing GeH4 gas in Example 5,
C2H4 gas was introduced from the 5 cylinder.

Sei 1! (Sample 6).

The film forming conditions at this time are as follows.

SiH420sccm C2H45secm F2 5secm He 40secm Internal pressure 800mTorr Substrate temperature 300'0 Distance between gas outlet and substrate 3cm After 3 hours of gas blowing 1 A-3i of about 1.0 pm was placed on the quartz glass substrate
A C:H:F film was deposited. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 gm) on the A-SiC:H:F film, sample 6 was placed in a vacuum cryostat, and the dark conductivity (CRD) was 600 nm.
m, conductivity (σp) when irradiated with light of 0.3 mw/cm2,
The optical band gap (Eg'
Pt) was measured respectively.

The value obtained is cr d = 8 x 10-13 s/cmc
rp=lX10-8s/cm Egapt=1.9 eV.

Example 7 While introducing SiH4 gas in Example 1, 10
A film was formed by introducing Si 2H6 gas from No. 3 cylinder (Sample 7).

The film forming conditions at this time are as follows.

SiH 420secm Si 2H65secm F2 5secm He 40secm Internal pressure 800mTorr Substrate temperature 300°C Distance between gas outlet and substrate 3cm At this time, strong blue light emission was observed near the gas outlet. After one hour of gas blowing, about 1.21 Lm of A-3i:H:F film was deposited on the quartz glass substrate. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing An interdigitated electrodes (gap length 200#Lm) on the A-3i:H:F film.

Sample 7 was placed in a vacuum cryostat, and the dark conductivity (c
rd), 600nm, 0.3 mw/cm2
The electrical conductivity (σp) upon irradiation with light and the optical band gap (E g'Pt) were measured by measuring optical absorption.

The obtained value is crd=7X I0-11s/Cm □ σp = 9X10-7s/
c mE g 0Pt = 1.65 eV.

Example 8 In Example 7, F2 gas was introduced, and Omon 2 was also introduced from the pump 107 to form a film (Sample 8).

The film forming conditions at this time are as follows.

SiH420secm Si 2H65secm F2 3secm (,122secm He 40secm □ 1: Internal pressure 800 m T O
r r1 ≧ Substrate temperature 300'0 When gas is flowed with a distance of 1t3cm between the gas outlet and the substrate,
Strong blue light was seen at the gas confluence. After blowing out gas for 1 hour, approximately 1.81 Lm of A- was deposited on the quartz glass substrate.
A Si:H:F:0 film was deposited. It was confirmed by electron and line diffraction that this film was amorphous.

After vacuum-depositing a comb pattern pattern (gap length 200 gm) of pattern A on the A-Si:H:F:C pattern film, sample 8 was placed in a vacuum cryostat, and the dark conductivity (σd) was 600 gm.
conductivity when irradiated with light of nm, 0.3 mw 70m2 (
σp), and the optical band gap (E g'Pt) was measured from the Jll constant of optical absorption.

The obtained value is crd = 8X 10-11s/cmσp=9X1
0-'s/. .

EgOPt = 1.70 eV Example 9 Instead of introducing SiH4 gas in Example 1, 10
SnH4 gas was introduced from a 2-cylinder cylinder, and a 11-year reaction was carried out (Sample 9).

The film forming conditions at this time are as follows.

SnH410sc10 5c 20secm He 40sccm Internal pressure 800mTorr Substrate temperature 300℃ Distance between gas outlet and substrate 4cm At this time, SnH
Luminescence was observed at the confluence of 4 gases and F2 gas. After blowing out the gas for 3 hours, about 1. A Sn:H:F film of OILm was deposited. When confirmed by electron beam diffraction, this film was found to be amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 ILm) on the A-5n:H:F film, it was placed in a vacuum cryostat as in Example 1, and the dark conductivity (σd) and optical absorption were measured. Optical bandgap (Eg'Pt
) were measured respectively.

The value obtained is σd = 3 x 10' s/c mEgOP
t = 0.80 eV'.

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

The r& film forming conditions at this time are as follows.

SiH 420 sec F2 2 sec He 40 sec Internal pressure 800 mTorr Distance between gas outlet and substrate 3 cm As in Example 1, strong blue light emission was observed at the confluence of SiH 4 gas and F 2 gas. After 3 hours of gas blowing, about 1.04 m of Si:H:F film was deposited on the quartz glass substrate. When the deposited film was measured by electron beam diffraction, the diffraction peak of Si was visible.
It was found that it was polycrystalline.

After vacuum-depositing Ai comb-shaped electrodes (gap length 200 ILm) on the Si:H:F film, the sample IO was placed in a vacuum cryostat, and the optical band was determined by measuring dark conductivity (σd) and optical absorption. The gap (Eg'P') was measured respectively.

The value obtained is σd=3X I 0-3s/cm EgOPt = 1.4eV Met.

Example 11 In addition to introducing SiH4 gas in Example 1, 10
SnH4 gas was introduced from the 4 cylinder and film formation was performed (
Sample 11).

The film forming conditions at this time are as follows.

SiH420sccm SnH45secm F2 3sccm He 40secm Internal pressure 800mTorr Substrate temperature 300°C Distance between gas outlet and substrate 3cm At this time, strong blue light emission was observed near the outlet of the gas blowout tube.

After 2 hours of gas blowing, approximately 2.2
A JLm A-SfSn:H:F film was deposited. It was confirmed by electron diffraction that this film was amorphous.

All interdigitated electrodes (
After vacuum deposition of a gap length of 2004 m), sample 11 was placed in a vacuum cryostat.

Dark conductivity (σd), 600 nm, 0.3 m w 70
The electrical conductivity (σp) upon irradiation with light of m2 and the optical band gap (E g'Pt) were measured by measuring optical absorption.

The obtained values were σd = 3XlO-8s/cm σp = 9X 10-as/cm Eg'Pt = 1.2eV Example 12 In Example 1, instead of SiH4 gas, All2 (
A cylinder filled with CH3)5 gas was connected to the connection port of a 102 gas cylinder, and a flow film was formed by bubbling AfL2(CH3)seHe gas (sample 12), the bubbling temperature was 60 °C. There were two cylinders, cylinders 101 and 106.

The conditions for S formation at this time are as follows.

He flow rate when bubbling An2 (CH3) 20secF2
5secHe flow rate flowed with F2 gas within 40 s c cm
Pressure 800mTorr
Substrate temperature Room temperature substrate
Distance between quartz substrate gas outlet and substrate 1
1i 3 cm At this time, light emission was observed from near the exit of the gas outlet to the substrate.

After 30 minutes of gas blowing, a 3000 An film was deposited on the quartz substrate.

The conductivity was almost the same as that of An produced by vacuum evaporation. In addition, the adhesion to the quartz substrate was determined by vacuum-deposited A and Q.
It was significantly better than the membrane.

Example 13 In Example 1, w(co)6 was used instead of SiH4 gas.
The pombe was a 102 gas cylinder.

Then, w(Co)s was bubbled with He gas to form a film (sample 13), and the bubbling temperature was 60°C.
℃. There were two He gas cylinders, 101 and 106.

The film forming conditions at this time are as follows.

He flow rate when bubbling W(Co)9 20 s e cmF2
Within 74 40 sec m of He flowing with 5 sec F2 gas
Pressure 800mTor
r Substrate temperature Room temperature Substrate Quartz substrate Distance between gas outlet and substrate: 111i 3 cm At this time, light emission was observed from near the exit of the gas outlet to the substrate.

After 30 minutes of gas blowing, 5000 W films were deposited on the quartz substrate. The conductivity was almost the same as that of the W film made by electron beam vacuum evaporation. Furthermore, the adhesion to the quartz substrate was significantly better than that of the An film obtained by electron beam evaporation.

Example 14 Instead of flowing SiH4 gas in Example 1.

Film formation was performed by flowing H2Se gas (Sample 14).

The film forming conditions at this time are as follows.

H2Se 20secF2
10sc105c
, 40sccm internal pressure 800
mTo r rsubstrate temperature 60
℃ Substrate Quartz substrate Distance between gas outlet and substrate When gas is flowed 3 cm,
Luminescence was observed from near the outlet of the gas blowing tube to the board.

Approximately 2 pm of S was deposited on the quartz substrate after 30 minutes of gas blowing.
E film was deposited.

As a result of electron beam diffraction, it was confirmed that the obtained Se film was amorphous.1. In addition, a comb-shaped A pattern electrode was deposited on the Se film by vacuum evaporation, and the dark conductivity was determined by the method described in Example 1.
(σd), electrical conductivity (crp) upon irradiation with light of 600 nm and 0.3 mw/cm2, and optical band gap (Eg'Pt) by measuring optical absorption.

The obtained value is cr d = 3 X IO-13s / c ma
r p = 2 x 10-8 s/c mEg'
Pt=2.1eV.

Example 15 Instead of introducing F2 in Example 1.

A film was formed by introducing ci2 gas from a 107 pump (Sample 15).

The film forming conditions at this time are as follows.

SiH420sccm CJ12 2sccm He 40sccm Internal pressure 800mTorr Substrate temperature 300℃ Distance between gas outlet and substrate fi3cm At this time, SiH
Strong light emission was observed at the point where the 4 gas and the CfL2 gas merged. After 3 hours of gas blowing, about 1 layer was deposited on 1 quartz glass substrate.
．． A-Si:H:C sentence pattern of 5JLm was deposited. It was confirmed by electron diffraction that this film was amorphous.

After vacuum-depositing a comb-shaped electrode (gap length 200 gm) on the A-Si:H:CfL film, sample 15 was placed in a vacuum taliostat, and the dark conductivity (CRD) was 6.
00 nm, conductivity when irradiated with light of 0.3 mw/Cm2 (
σp), and the optical band gap (E g'Pt) was measured by measuring optical absorption.

The value obtained is crd=2X10=I+s/cm σp=6X10-85/Cm EgOPt=1.70eV Met.

〔effect〕

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

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a film forming apparatus used in an example of the present invention. 101-108---------------Gas cylinder. 101a to 108a---------Gas introduction pipes. 101b~l O8b------mass flow meter,
101c -108c------------Gas pressure gauge. 101d N108d and 101e Nl 08 e----------------------
----- Valve. 101 f -108f----------------------
- One pressure gauge. 109, 110, 111----1---Gas introduction pipe, 112--1------------------
- One-substrate holder. 113------------Heater for heating one substrate, 116---Thermocouple for monitoring substrate temperature, 11 B------------ −−−−−−−−
---------1-----Substrate, 119--1--
−−−−−−−−−−−−−−1 Vacuum exhaust valve. respectively.

Claims (18)

[Claims] (1) A gaseous raw material for forming a deposited film and a gaseous halogen-based oxidant having the property of oxidizing the raw material are introduced into a reaction space and brought into chemical contact to bring them into an excited state. A deposited film is formed on a substrate located in a deposition space by generating a plurality of precursors including precursors of and using at least one of these precursors as a source of a deposited film component. Deposited film formation method. (2) The deposited film forming method according to claim 1, which accompanies light emission 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 linear silane compound. (5) The linear silane compound has the general formula Si_nH_
The deposited film forming method according to claim 4, which is represented by 2_n_+_2 (n is an integer from 1 to 8). (6) The deposited film forming method according to claim 3, wherein the chain silane compound is a branched chain silane compound. (7) The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure. (8) The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound. (9) The linear germane compound has the general formula Ge_mH_
The deposited film forming method according to claim 8, which is represented by 2_m_+_2 (m is an integer of 1 to 5). (10) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound. (11) The deposited film forming method according to claim 1, wherein the gaseous raw material is a tetrahedral compound. (12) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains 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 deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent is a gas containing fluorine atoms as a constituent component. (16) The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state. (17) The deposition according to claim 1, wherein the substrate is disposed at a position opposite to the direction in which the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space. Film formation method. (18) The deposited film forming method according to claim 1, wherein the gaseous raw material and the gaseous halogen-based oxidizing agent are introduced into the reaction space from a transport pipe having a multi-tube structure.