JPH01100010A - Noncrystalline hydrogenated silicon fine particle film and production thereof - Google Patents

Abstract

PURPOSE:To provide the titled film containing noncrystalline hydrogenated silicon fine particles at or below a specified size, with its infrared absorption spectra specified to enable the emission of the bound hydrogen corresponding to the fine particle size by external energy. CONSTITUTION:The objective film contains noncrystalline hydrogenated silicon fine particles with a size of <=1mu, having such infrared absorption spectra as to give absorption in the range from 2,080-2,150cm<-1> with the absorption peak intensity near 2,000cm<-1> being <=50% of that in said range. This film contains great quantities of bound hydrogen, being capable of emitting such amount of bound hydrogen as to correspond to fine particle size by external energy. This film can be obtained, using a plasma CVD apparatus, by generating the discharge plasma or a gas containing silane and its derivative followed by jetting the resultant plasma product through a nozzle against the substrate taking advantage of pressure difference to effect deposition on it.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to amorphous hydrogenation using the high concentration of bound hydrogen contained in amorphous hydrogenated silicon ultrafine particles and the ease of hydrogen release. The present invention relates to a fine particle film made of silicon ultrafine particle aggregates and a method for producing the same.

[Conventional technology]

As fine particles of hydrogenated silicon containing SiH2 bonds and a high concentration of hydrogen, there are conventionally known particles shown in Japanese Patent Publications No. 62-32122, No. 62-32121, and the like.

All of these hydrogenated silicon fine particles were determined by infrared absorption spectroscopy to be -(SiH2), around -2100cm-', around =SiH22110cm-', and -3iH321
It is shown that each base group is around 40 cm-'.

Also, -(SiH2)ゎ-, =SiH2 and a small amount of -3
As for the use of hydrogenated silicon fine particles containing each group of iH3, Japanese Patent Publication No. 62-32122, 62-3
2121, etc., it has been shown that it can be used for storing and desorbing hydrogen.

In addition, a substance in which no =Si-H bond (2000 cm-') is recognized and has only =SiH2 bonds and -SiH3 bonds is described in Japanese Patent Publication No. 32128/1982, but this substance is In addition to bonded hydrogen (=SiH2, -8iH3) bonded to Si atoms on the surface, non-bonded hydrogen is S
It is characterized by being contained in a large amount in the i-crystal lattice and being Si crystal fine particles.

In addition, this material can drive out hydrogen atoms that are not chemically bonded to Si by simply heating them to 100 to 150°C, and the hydrogen atoms can drive out free hydrogen that is not bonded to Si by 45 to 7
It contains as much as 0 at%.

The following method is known as a method for producing a substance mainly having a peak around 2100 cm-'.

1. A method of thermally decomposing a mixed gas of SiH4 and H2 at high temperature and depositing a uniform film on a substrate kept at a substrate temperature lower than the gas temperature (referred to as HOMOCVD method).B.
A, 5cott et al., Appl, Phys.

Lete, 39. 74 (1982) 2, a method of lowering the substrate temperature and decomposing a mixed gas of Si 2 H 6 and H 2 by the glow discharge (GD) method (low temperature - disilane -
(referred to as GD method) J, Appl, Phys, 58
．． 4658.1985゜3, method of sputtering (sp) St in H2 gas while lowering the substrate temperature (referred to as low temperature-reactive SP method), Japanese Patent Publication No. 62-
(No. 32122, No. 62-32121, etc.) Here, the material obtained by the HOMOCVD method is a normal uniform film, and the analysis result of infrared spectroscopy (IR) is 2100 cm-'
In addition to nearby peaks, it clearly includes a peak around 2000 cm-' (attributed to SiH).

Further, the film obtained by the low temperature-disilane-GD method is also a normal film, and it has been shown that the results of IR analysis vary depending on the substrate temperature.

That is, at room temperature, in addition to the peak around 2100 cm-', it clearly includes a peak around 2000 cm-'. At liquid nitrogen temperature (77K), the peak mainly appears around 2100 cm-', but it is still a normal film.

Although the substance obtained by the low-temperature-reactive SP method mainly has a peak at 2100 cm-' according to the results of IR analysis, it is disclosed that the substance obtained is Si crystal fine particles.

[Problem that the invention is trying to solve] However,
In the conventional example above, the amount of hydrogen in silicon hydride is determined by the amount of hydrogen contained (the amount of hydrogen occluded in fine particles) determined by gas chromatography and the amount of bonded hydrogen (combined as Si-In bonds) determined by infrared absorption spectroscopy. amount of hydrogen, n=
1.2.3), a significant amount of hydrogen is present in the material in the form of free hydrogen (as shown by the data) in hydrogenated silicon fine particles.

Therefore, it is suitable as a hydrogen storage material for the purpose of absorbing and desorbing hydrogen, but when using it by desorbing hydrogen using external energy (e.g., heat, light, laser light, electron beam, X-ray, etc.) had the following drawbacks.

1. I could not think of using it in the form of a film.

2. Since free hydrogen exists in the fine particles, hydrogen release in response to external energy was not uniform.

In addition, in conventional examples regarding manufacturing methods, 1) the HOMOCVD method does not yield a substance that mainly has a peak around 2100 cm-', and 2) the low-temperature-disilane-GD method produces a substance that mainly has a peak around 2100 cm''. Obtaining the material required the substrate to be at liquid room temperature and the use of disilane. 4) Low temperature-reactive SP
Even with this method, it was necessary to bring the substrate to liquid nitrogen temperature in order to obtain a substance mainly composed of 2100 cm-'.

Furthermore, the conventional example had the following drawbacks.

1. In the conventional example described above, although it is possible to obtain a normal film or a crystalline fine particle film, there is a drawback that an amorphous ultrafine particle film cannot be obtained as in the present invention.

2. In addition, in the low-temperature-disila-GD method, a substance with a peak around 2100 cm-' can only be obtained when the substrate is cooled with liquid nitrogen and disilane, which is much more expensive than silane, is used. Because it can withstand liquid nitrogen temperatures, it can only be deposited on substrate materials. The disadvantage is that it is difficult to deposit on materials that are brittle at liquid nitrogen temperatures, such as plastic films.

3. In the low-temperature-reactive SP method, a substance mainly composed of 2100 cm-' is obtained only when the substrate is cooled with liquid nitrogen, so it can be deposited only on substrate materials that can withstand liquid nitrogen temperature.

Therefore, it had the same drawbacks as the low temperature-disilane=GD method.

Therefore, the purpose of the present invention is to provide a fine particle film containing amorphous hydrogenated silicon fine particles capable of releasing hydrogen by external energy.

Another object of the present invention is to provide a fine particle film containing amorphous hydrogenated silicon fine particles having a bonded hydrogen release ability depending on the size of the fine particles.

Still another object of the present invention is to provide a novel method for producing amorphous hydrogenated silicon fine particle film that can be deposited at high speed.

[Means and effects for solving the problems] The above objects are achieved by the present invention as described below.

That is, the present invention provides a fine particle film containing 1 μm amorphous hydrogenated silicon fine particles, the infrared absorption spectrum of the film having absorption in the range of 2080 to 2150 cm-', and
Absorption peak intensity near 0 cm-1 is 2080-2150
The present invention is an amorphous hydrogenated silicon fine particle film characterized by an absorption peak intensity of 50% or less of cm-' absorption peak intensity.

Furthermore, the present invention involves generating a discharge plasma of a gas containing silane and its derivatives, and ejecting the resulting plasma product from a nozzle toward a substrate using a pressure difference to deposit it on the substrate. This is a method for producing a characteristic amorphous hydrogenated silicon fine particle film.

The size of the amorphous hydrogenated silicon ultrafine particles in the present invention is 1000 Å or less, preferably 500 Å or less.

Although the shape of the ultrafine particles is not particularly important, it is more effective to use particles that are relatively close to each other and of uniform size.

Although the lower limit of the particle size is unknown, it can be
According to the observation results obtained by M), the effect was observed even with particles having an average particle size of 100 Å or less, which is several dozen people.

The amorphous hydrogenated silicon ultrafine particles and their aggregates in the present invention differ from the substance described in Japanese Patent Publication No. 62-32128 in the following points.

1. Hydrogen content (hydrogen content contained in ultrafine particles and their aggregates) determined by gas chromad method and infrared spectroscopy (IR)
The amount of bonded hydrogen determined by the method (amount of hydrogen bonded as a Si--Hn bond, n=1°2.3) was almost the same, and the amount of hydrogen was about 70 atom %.

2. The hydrogen release temperature determined by the heating gas chromatography method is 1
The temperature was 70-450°C. Furthermore, the amount of hydrogen released at temperatures above 450°C was smaller than the amount released at temperatures of 170 to 450°C. (Figure 2) This seems to reflect the situation in which the bond between Si and H dissociates.

3. The new substance according to the present invention is determined from the chart diagram (Figure 3) by infrared absorption spectroscopy: -("1Hz), l + = SiH
It was a film of ultrafine particles and their aggregates containing 2 bonds and SiH3 bonds.

4. Also, according to X-ray diffraction, the pattern indicating the crystallinity of St (the pattern seen around 2θ28°) was small or almost absent, and it was found to be composed of microcrystals or amorphous. .

5. According to the method of the embodiment proposed by the present inventors, which will be described later, a film made of ultrafine amorphous silicon particles and their aggregates having the above-mentioned physical properties can be easily obtained.

Since the amorphous hydrogenated silicon ultrafine particle aggregate film of the present invention is formed from ultrafine particles, it is easy to heat it by irradiating energy from the outside because the ultrafine particles have extremely poor thermal conductivity compared to a uniform film. It was experimentally determined that hydrogen is released when the hydrogen release temperature is reached.

The external energy used in this case is not particularly limited as long as it can be converted into thermal energy by irradiation.

In addition, the novel amorphous hydrogenated silicon ultrafine particles of the present invention and their aggregate film, which have good hydrogen release characteristics due to heat, have I
From the measurement results using the R method, it was found that the sharper the peak around 2100 cm-' (or even a single peak), the easier the hydrogen release.Especially, the peak around 2000 cm-'
-SiH bond) intensity I201
50% or less, i.e. I 2000 / I 21000
≦0, 5, hydrogen release is easy, preferably I 2100 / I 2+00 ≦ 0.3, more preferably I 2000 / I 2100 ≦ 0.1.

The above are the characteristics of the amorphous hydrogenated silicon ultrafine particle film obtained by the present invention.

Since materials with such physical properties contain hydrogen atoms in a bonded state, they do not release hydrogen at all under normal conditions and atmospheres, and hydrogen is released only when irradiated with external energy. For example, an example in which thermal energy is used is shown in FIG.

As can be seen from FIG. 2, hydrogen-resistant release occurred, which was determined to be due to bond dissociation.

Therefore, when the substance of the present invention is used, hydrogen is released only when irradiated with external energy, so it can be used as a stable hydrogen storage material.

In addition, since the fine particles of the fine particle film obtained in the present invention are amorphous, compared to polycrystalline or crystalline ones, hydrogen is evenly dispersed in each particle, so hydrogen is released from each fine particle. I can do things.

That is, it is possible to create a negative unit of hydrogen release area according to the size of the fine particles. This can be used to write high-density information using external energy.

As a manufacturing method for obtaining a film-like material comprising ultrafine amorphous hydrogenated silicon particles and their aggregates according to the present invention,
Plasma CVD as disclosed in Publication No. 221377
A method using a device can be used.

That is, as an apparatus for obtaining a film-like material made of ultrafine amorphous hydrogenated silicon particles and aggregates thereof according to the present invention, for example, the first
The equipment shown in the figure can be used.

In Fig. 1, 1 is the contraction/expansion nozzle, 2 is the throat of the nozzle, 3 is the upstream chamber, 4 is the downstream chamber, 5 is the cavity resonator, 6 is the base, 7 is the microwave input window, 8 may be directly connected to the exhaust pump 5. When a reaction gas is introduced into the cavity 5 through the chamber 12, the reaction occurs inside the cavity 5, and the chamber 5 acts as a reaction chamber.

For example, when making a-3i fine particle film, SiH4 gas and, if necessary, H2 gas are fed through the gas inlet 12, plasma is generated in the reaction chamber, the gases are decomposed and reacted, and plasma products are obtained. .

Note that the plasma product in the present invention is a general term for fine particles and active species generated in plasma, regardless of whether they are reacted or unreacted.

Then, this is blown out from the nozzle 4 together with partially unreacted gaseous active species and blown onto the substrate 6 to be fixed thereon.

As means for imparting energy to the plasma, electromagnetic waves such as microwaves, ultraviolet rays, or high frequency waves such as RF waves, low frequency waves, and electric field application such as direct current can be used. Ultraviolet rays or microwaves are easy to use in practical applications, and although it is necessary to devise the shape of the reaction chamber in this case, there is no need to place structures such as electrodes inside the reaction chamber, and there is no need to use a window for energy input. It's good to have. There are various ways to use microwave plasma, such as Japanese Journal using a coaxial tube.
al of Applied Physics
21 (8) L470 (1982), J. Non-Crystalline 5o
There are methods such as those seen in lids 77 & 78,
From the standpoint of obtaining efficient plasma products, reaction chamber 5
A method using a microwave cavity resonator is very effective. FIG. 4 is a diagram showing an example of a cylindrical cavity resonator, and T
Once the microwave frequency that defines the electric field distribution in the E112 mode is determined, a design can be made according to a known method. Microwave resonance is T E +o
This is effective for high-speed deposition of a particulate film, especially when the plasma products are particulates. This can be achieved by setting the axial length l of the cavity resonator to 1/2 of the resonant wavelength λ. By increasing the length of the cavity resonator, l=λ
The comparison of the deposition rate with the case of λ is shown in the second graph, which shows that as the SiH4 concentration is increased, the increase in the deposition rate reaches a plateau in the case of l=λ! In the case of =λ/2゛, such a limit is not recognized and it can be seen that it increases linearly (Figure 5). It was confirmed that when 1>2λ, the deposition rate becomes extremely slow and is not practical. Therefore, the length l of the cavity resonator must satisfy the condition l≦3λ/2.

Furthermore, as the pressure is increased, the deposition rate increases as shown in the example in Figure 6 (If the pressure is increased to 1.0 Torr or higher, the deposition rate increases by 1μ/
High-speed deposition on the order of sec is also possible. The nozzle is provided to blow out a gaseous substance containing products generated in the plasma at high speed, and to spray it onto the substrate and fix it. Next, the shape of the nozzle can generally be any shape, but in order to increase the adhesion of the plasma products to the substrate, and to convert the plasma products into a beam and efficiently collect them on the substrate, it is necessary to It is desirable to use a supersonic nozzle with a so-called contraction-expansion type aperture change. Its cross-sectional shape is not limited to a circular shape, but various modifications such as those shown in Japanese Patent Application Laid-Open No. 61-221377 can be used depending on the purpose.

The area near the base chamber downstream from the nozzle is usually 10-3 TOr.
Use the force less than r. It is desirable that the pressure difference between the upstream side of the nozzle and the downstream side of the nozzle ranges from several lO to about 100.

The substrate can be silicon wafer, glass, Nesa glass, plastic, metal, or many other materials.

The shape may be flat or other shapes. If the substrate was heated during deposition, a change in the amount of bound hydrogen in the resulting film was observed, but even when the substrate was heated to 400° C., the entire amount of bound hydrogen did not escape.

The above are the characteristics of the manufacturing method for obtaining an amorphous silicon ultrafine particle film of the present invention.

In the present invention, Si
S i H4, S i2 H6, S i3 as sources
Si hydride such as Hs, SiF4, Si2F
6, 5iSi halide such as CA' 4, 5i
HF3, SiH2F2.

Compounds made of Si, hydrogen, and halogen such as 5iH2Cj72 can be mentioned. In the present invention, it may be used diluted with H2 gas, but when used in combination with Si source and hydrogen for dilution, there are the following advantages:
When the temperature was set to 5Q or less, there was no fogging caused by this in the cavity.

For example, inject 3% H2 gas into the cavity resonator 5 shown in FIG.
Flow SiH4 gas diluted to
When the power was set to 50W, as shown in Figure 6, -(Si
H2) Despite the fact that amorphous silicon hydride containing mainly n- was obtained, fogging did not occur on the quartz window for introducing microwaves under any conditions.

Note that similar effects have been obtained when other dielectric conductors such as alumina are used as the window for introducing microwaves.

As described above, the method for producing an amorphous silicon ultrafine particle aggregate film disclosed in the present invention is a novel method for producing an ultrafine particle aggregate film that could not be obtained by conventional production methods, and at the same time This manufacturing method enables high-speed film formation without contaminating the dielectric film, and is suitable for mass production with extremely good reproducibility.

〔Example〕

The present invention will be specifically described below with reference to Examples.

Example 1 An amorphous silicon ultrafine particle aggregate was formed into a film on a substrate using the apparatus shown in FIG. The device shown in FIG. 7 is basically the same as the device shown in FIG. 1, but differs from that in FIG. 1 in that a contraction/expansion nozzle is attached directly to the tip of the cavity resonator.

In FIG. 7, 21 is a contraction/expansion nozzle, 21a is a nozzle inlet, 21b is a nozzle outlet, 22 is a nozzle throat, and 23 is a permanent magnet cylinder placed around the contraction/expansion nozzle, with N pole in the axial direction of the nozzle. The nozzle is filled with bar magnets so that the S and S poles are lined up and a coaxial magnetic field is applied around the nozzle.

24 is a downstream chamber, 25 is a cylindrical cavity resonator that also serves as a reaction chamber, 26 is a substrate holder with a built-in heater, 27 is a glass substrate, 28 is a quartz window for introducing microwaves, 29 is a microwave waveguide, 30 31 is a gas introduction pipe, and 31 is an exhaust system. The microwave oscillator 29 was attached to the side opposite to the cavity resonator, and was used with an oscillation frequency of 2.45 GHz and a pulse oscillation output of 1 kW.

The magnet 23 helps generate and maintain plasma at the nozzle inlet. The nozzle 21 has a cross-sectional area of the nozzle population 21a and a throat portion 22.
The ratio to the cross-sectional area of is 31. The ratio of the cross-sectional area of the nozzle outlet 21b to the cross-sectional area of the throat portion 22 was 7, and it was made of polytetrafluoroethylene (PTFF).

The cavity resonator was made of stainless steel (SUS), and its axial length l was set to l/2 of the resonance wavelength λg.

The following operations were performed to obtain a film composed of amorphous silicon ultrafine particle aggregates.

First, after fixing the Si wafer as a base to the holder 26, the inside of the downstream chamber 24 is heated to 2X10-'Tor using the exhaust system 31.
The pressure was reduced to r. Next, SiH4 diluted to 3% with N2 gas
Flow rate 11 of the gas from the gas introduction pipe 30 into the cavity resonator 25
It was run at 005CC. Then, the pressure inside the cavity resonator is 4
X10-'Torr, from the nozzle 21 to the downstream chamber 24
I burst out laughing. At this time, the pressure in the downstream chamber 24 is 4.5
It became about 10-'Torr. Next, a discharge plasma was generated in the cavity resonator 5 by feeding it from a microwave oscillator through the microwave waveguide 29 through the quartz window 28 and into the cavity resonator 5.

The power of the microwave was 150W. Then, fine particles are formed in the plasma and blown out from the nozzle 21 together with the remaining gas components, forming a fine particle beam that advances through the downstream chamber and collides with the base body 27 to be fixed.

The thickness of the layer of ultrafine particle aggregates deposited on the substrate was 7.5 μm after 5 minutes of discharge. No heating of the substrate was performed.

After depositing the ultrafine particle aggregates, the gas was stopped, the downstream chamber 24 was sufficiently evacuated, the vacuum was leaked with N2, and the film-formed substrate was taken out and immediately stored in an N2 atmosphere.

The ultrafine particle aggregate film was deposited on the substrate as a glossy film with a yellowish brown appearance, and was deposited in the shape of a disk centered at the center of the beam. It was also thickest in the center.

When this ultrafine particle aggregate film was measured by Fourier transform infrared spectroscopy (FT-IR) in an atmosphere where N2 was passed through, there was a sharp single peak near 2100 cm-', and 9 others.
05 cm m-' around 860 cm-' and 650 c
It had a peak near m-'. (Figure 1) Therefore,
-(SiH2) n (around 2100 cm-') as the main component, SiH2 (around 860 cm-') and SiH3 (9
It was found that SiHWag
It was also found that the film was different from conventional amorphous hydrogenated silicon films because the gingmode appeared at 650 cm-'.

Subsequent SEM observation revealed that this film-like substance had a diameter of 1
It has a structure in which ultrafine particles of relatively uniform size of approximately 00' to 200 particles are deposited, and the presence of the microparticles was confirmed both on the surface and cross section of the film-like material.

According to SEM observation, the ultrafine particle aggregates appeared to be quite densely deposited.

Next, when examining the X-ray diffraction pattern, Si showed only a small pattern that seemed to contain microcrystals.

The above measurements were carried out in a N2 atmosphere or under a vacuum that was evacuated after N2 flow, taking into consideration the reactivity of the =SiH2 bond in air. After completing all the above measurements, the remaining sample was measured by FT-IR, but there was no change from the initially measured spectrum.

In addition, in this example, SiH4 diluted to 3% with N2 gas
Since gas was used, no fogging of the quartz window 28 for microwave injection occurred.

Next, the amorphous hydrogenated silicon ultrafine particle aggregate film mainly composed of -(SiH2)n- obtained in this example was treated with an Ar+ laser (λ=488 n
m), a difference in light reflectance was observed between the laser beam irradiated area and the non-irradiated area in both cases. This difference in reflectance is sufficiently visible, and moreover, Ar
+ Photoluminescence was generated during laser irradiation. Incidentally, as the Ar'' laser irradiation was continued in the atmosphere, it was observed that the luminescence (photoluminescence) intensity increased.

Separately, FT-IR measurements of the amorphous hydrogenated silicon ultrafine particle film after being left in the atmosphere revealed the presence of bonds containing oxygen.

Comparative Example A film was formed on a Si wafer substrate 31 using a glow discharge device having a 20'φ parallel plate type counter electrode shown in FIG.

At this time, the substrate was not heated, SiH4 diluted to 70% with N2 was used as the source gas, and the gas flow rate was 203 CCM.

At this time, the pressure in the discharge chamber 31 is maintained at 0.11 Torr,
When a film was formed on the substrate 31 provided on the at electrode 32 by generating plasma with RF power of 50 W, a uniform film could be formed without generating fine particles.

After the film was formed, when observed with SEM, no structure like that seen in the ultrafine particle aggregates (Example 1) was observed on the surface or cross section of the film, confirming that it was a uniform film. .

Next, when this uniform film was subjected to FT-IR measurement, a spectrum diagram as shown in FIG. 9 was obtained.

As can be seen from Fig. 9, the uniform film obtained was -SiH bond (2
000 cm-'), and X-ray diffraction results showed that it was amorphous without containing microcrystals.

Next, this uniform film was irradiated with an Ar+ laser (λ = 488 nm), but obliquely incident light was applied between the laser irradiated area and the non-irradiated area to observe the difference in light reflectance, but most of the light was not reflected. No difference in rate was observed, and no light emission (photoluminescence) was observed during Ar+ laser irradiation.

Examples 2 to 9 A film was formed on a substrate by a method similar to Example 1 using the apparatus shown in Figure A. Table 1 summarizes the implementation conditions of each example and the characteristics of the obtained amorphous silicon ultrafine particle aggregates.

In Examples 2 to 8, the deposition rate changed depending on the preparation conditions,
The particle size also changes accordingly, but all films are amorphous (containing microcrystals) silicon hydride ultrafine particle aggregate films, and there are differences in degree depending on Ar + laser (λ = 488 nm) irradiation. observed light emission (photoluminescence).

In Example 9, although a decrease in the deposition rate was observed, the grain size of the obtained film was judged to be discolored by ~20 people, but -(SiH2
), -, and was amorphous (including microcrystalline) hydrogenated silicon.

〔Effect of the invention〕

As explained above, according to the present invention, amorphous hydrogenated silicon, which could not be obtained easily in the past, can be obtained, and furthermore, this material contains a large amount of bound hydrogen. Therefore, it can be used as a hydrogen-releasing material that is normally stable but releases hydrogen when heated, and as a material that releases hydrogen only from the irradiated area when irradiated with a laser.

Since the fine particle film of the present invention is mainly composed of -(SiH2), -, the optical band gap is 2.0 to 2.0.
It has a voltage of 4 eV and emits room temperature light (photoluminescence) using a short wavelength laser, so it can also be used as a light emitting material.

According to the present invention, it is possible to form amorphous silicon hydride mainly composed of -(SiH2)n- at high speed, and since it is deposited in a beam form, other parts of the deposition chamber are not contaminated, making it extremely suitable for mass production. A method is provided.

[Brief explanation of the drawing]

Fig. 1 is a diagram showing an example of the apparatus used to create the amorphous hydrogenated silicon ultrafine particle aggregate film of the present invention, Fig. 2 is a diagram showing the results of thermal analysis by the heating gas chromad method, and Fig. 3 The figure shows FT of an amorphous hydrogenated silicon aggregate film obtained by the present invention.
- A diagram showing the analysis results by IR method, Figure 4 is a diagram showing the electric field distribution in the cavity resonator which becomes the plasma generation chamber, and Figure 5 is a diagram showing the relationship between the SiH4 concentration in H2 and the film formation rate. , FIG. 6 is a diagram showing the relationship between the pressure inside the cavity resonator and the film formation rate, and FIG. 7 is a diagram showing the relationship between the film formation rate and the pressure inside the cavity resonator. Figure 8 is a diagram showing an example of a parallel plate type glow discharge device for producing a uniform film, and Figure 9 is a diagram showing the F of a uniform film obtained with the device shown in Figure 8.
It is a figure showing the analysis result by T-IR method.

Claims (2)

[Claims] (1) A fine particle film containing amorphous hydrogenated silicon fine particles of 1 μm or less, the film having an infrared absorption spectrum of 20
It has absorption from 80 to 2150cm^-^1 and 200cm
Absorption peak intensity near 0cm^-^1 is 2080-21
An amorphous hydrogenated silicon fine particle film characterized in that the absorption peak intensity is 50% or less of the absorption peak intensity at 50 cm^-^1. (2) The feature is that a discharge plasma of a gas containing silane and its derivatives is generated, and the resulting plasma product is ejected from a nozzle toward a substrate using a pressure difference and deposited on the substrate. A method for producing an amorphous hydrogenated silicon fine particle film.