JP3462976B2 - Method for producing silicon particles and method for forming silicon film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a silicon film used for an LSI, a thin film transistor, a photoelectric conversion device, and a photoconductor, and a method for producing silicon particles.

[0002]

2. Description of the Related Art Conventionally, polycrystalline silicon (hereinafter poly-Si)
As a method of forming a film or an amorphous silicon (hereinafter a-Si) film, thermal CVD (Chemical Vap) using silane gas is used.
or Deposition) method, plasma CVD method, optical CVD method, etc. are generally used, and thermal CVD is generally used for poly-Si films.
For the a-Si film, the plasma CVD method is widely used for mass production.

As a CVD method using a high-order silane gas, a method of thermally decomposing a high-order silane gas under a pressure of atmospheric pressure or higher, a method of thermally decomposing a cyclic silane gas, a method of using a branched silane gas, or a high-order silane gas higher than trisilane is used. A method of performing thermal CVD with silane gas at 480 ° C. or lower has been proposed.

However, all the films that can be formed by the CVD method using these higher order silane gases are a-Si films, and these CVD methods have the following problems.

Since the gas phase reaction is used, particles are generated in the gas phase, which causes problems such as contamination of the apparatus and reduction of the device yield. Since the raw material is used in a gaseous state, it is difficult to obtain a film having good step coverage on a substrate having an uneven surface. The film formation rate is slow and the throughput is low. The plasma CVD method requires a complicated and expensive device such as a high frequency generator. Expensive high vacuum equipment is required.

Therefore, in order to avoid the problems (1) to (3), a method of using a liquid higher order silane instead of a gas phase reaction has been proposed in JP-A-7-267621.
In the method described in the publication, a liquid high-order silane is coated on a substrate, then heated, and a thermal history including a temperature rising process is performed to cause a decomposition reaction in the coating film to form a silicon film on the substrate. To form.

In order to obtain an a-Si film by this method, the ultimate temperature may be set to about 550 ° C. or lower, but to obtain a poly-Si film having characteristics that can be used in electronic devices and photoelectric conversion elements, 700 ° C.
The above high temperature is required.

Therefore, in order to lower the formation temperature, for example, JP-A-6-296020 proposes a method using a Ni catalyst. Specifically, Ni on the substrate
After depositing a thin film, deposit a-Si on Ni and heat-treat it
By forming poly-Si using i as a nucleus, the temperature can be lowered to about 600 ° C or lower.

Recently, powdered silicon has come to be used as a raw material for manufacturing a silicon substrate, but in this case, a high temperature of 600 ° C. or higher by the fluidized bed method is required.

As a method for obtaining silicon particles other than the fluidized bed method, a general formula SiH _x (OR) _4-x (x = 0, 1,
2, 3 and R are CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ) alkoxysilane represented by the general formula Si _y H _{2y + 2} (y = 1,
The silane represented by 2 and 3) is mixed and pressurized to form silicon without heating.

[0011]

However, inexpensive glass, which is effective for cost reduction, and flexible polymer film, which has a wide range of device applications, softens or melts at a temperature of 600 ° C. or higher. Therefore, the conventional method (requires a temperature of 600 ° C or higher) is used for these materials.
There is a problem that it cannot be used as a substrate when forming a poly-Si film.

Further, if the Ni catalyst is used, the heat treatment temperature can be lowered as described in the prior art, but in this case, there remains a problem that Ni remains in the film and the process is complicated.

The present invention solves the above problems when a silicon film is formed from liquid high-order silane without using a substance such as Ni that can be an impurity, and its purpose is low. An object of the present invention is to provide a method for forming a poly-Si film that is cost-effective, simple, and can be formed at low temperature.

The present invention also has a general formula Si _y H _{2y + 2} (y = 1, which is a gas at room temperature) from the viewpoints of explosiveness and ignitability.
Si _n H _{2n + 2} or Si _n H _2n (n is an integer of n ≧ 4) that is easier to handle than silane represented by 2 and 3)
It is intended to provide a method for producing silicon particles excellent in particle property, which does not require high temperature using a liquid high-order silane represented by.

[0015]

The method for producing silicon particles according to the present invention comprises a liquid high-order silane represented by the general formula Si _n H _{2n + 2} (n is an integer of n ≧ 4) and a general formula SiR.
¹ _m (OR ² ) _4-m , (where m is an integer of 0 to 3, R ¹ is hydrogen or an organic group, R ² is an organic group, but when m ≧ 2, a plurality of R ^1's are different from each other. Or a plurality of R ^{2 s} may be different groups when m ≦ 2),
Alternatively, the general formula (R ² O) _3-m R ¹ _m Si (SiR ³ ₂ ) _j S
iR ¹ _k (OR ² ) _3-k , (note that m is an integer of k = 0 to 2,
j is an integer of j ≧ 0, R ¹ and R ³ are hydrogen or an organic group, R ²
Is an organic group, but R ³ may be different groups, and when there are a plurality of R ¹ , they may be different groups, and when there are a plurality of R ² , they may be different groups). The alkoxysilane represented or the general formula (R ²
O) _3-x R ¹ _x Si (Si _y R ^{3 2} _y ) O (Si _z R ³ _{2 z} ) Si
R ¹ _w (OR ² ) _3-w {W, x is an integer from 0 to 3 (however, w and x are not 3 in particular), y and z are y, and z ≧ 0.
Is an integer, R ¹ and R ³ are hydrogen or an organic group, R ² is an organic group,
However, R ³ may be different groups, and when there are a plurality of R ¹ , they may be different groups, and when there are a plurality of R ² , they may be different groups. After mixing or contacting with siloxane, pressure is applied to form silicon particles.

During the formation of silicon particles, JP-A-6-21
In the 9724 publication, the general formula Si _y H _{2y + 2} (y = 1,
While uses a silane represented by 2, 3) in the present invention, the general formula Si _n H _{2n + 2 (n} uses a liquid high-order silane represented by an integer) of n ≧ 4 .

In the method for forming a silicon film according to the present invention, after silicon particles are formed from a part of a raw material of higher order silane and alkoxysilane or alkoxysiloxane, the remaining alkoxysilane or the remaining alkoxysiloxane is evaporated, Energy is given to decompose the unreacted residual higher silane, and the silicon particles serve as nuclei.
Grow poly-Si film.

In the method for forming a silicon film according to the present invention, the decomposition of higher order silane and the growth of the silicon film may be carried out in the presence of atomic hydrogen. In that case, the characteristics of the obtained poly-Si film as an electronic material can be further improved.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for producing silicon particles and the method for forming a silicon film according to the present invention will be described below.

The liquid high-order silane used in the present invention has a general formula Si _n H _{2n + 2} or Si _n H _2n (n is an integer of n ≧ 4).
It is represented by. Table 1 shows the boiling points and melting points of typical high order silanes.

[0021]

[Table 1]

Although not shown in Table 1, Si _{n
H 2n + 2, Si n H} 2n (n is an integer of n ≧ 8) higher silane of difficult to coat in order to coagulate at temperatures below room temperature. Therefore, higher order silanes used in the coating solution at a temperature below room _{temperature, Si n H 2n + 2 (} n is an integer of 4 ≦ n ≦ 7) used those represented by. Specifically, normal tetrasilane (n-Si ₄ H ₁₀ ) and normal pentasilane (n-S
i ₅ H ₁₂ ), normal hexasilane (n-Si ₆ H ₁₄ ),
Normal peptasilane (n-Si ₇ H ₁₆ ) or isomers thereof can be used.

The higher silane used in the coating solution at a temperature below room temperature, Si _n H _{2n (n} is an integer of 4 ≦ n ≦ 7) may be used those represented by. Specifically, cyclotetrasilane (Si ₄ H ₈ ), cyclopentasilane (Si ₅ H ₁₀ ),
Cyclohexasilane (Si ₆ H _12), cycloheptasilane (Si ₇ H _14), or can also be used these isomers.

Of course, if the temperature of the atmosphere is raised, Si
If _{n H 2n + 2, Si n} H 2n (n is an integer of n ≧ 8) temperature higher silane is a liquid, a can of course can be applied. Moreover, as shown in FIGS. 2 to 5, the ambient temperature can be easily raised by the configuration of the apparatus used in the present invention.

The alkoxysilane used in the present invention is represented by the general formula SiR ¹ _m (OR ² ) _4-m . In the above general formula, m = 0 to 3; R ¹ is hydrogen or an organic group; R ² is an organic group; however, when m ≧ 2, a plurality of R ^1's may be different groups. Multiple R when ≤2
² may be different groups.

Alternatively, the alkoxysilane used in the present invention has the general formula (R ² O) _3-k R ¹ kSi (Si _j R ³ _2j ) Si.
It is represented by R ¹ _h (OR ² ) _3-h . In the above general formula, h and k are integers of 0 to 3 (however, h and k are not 3 at the same time), j is an integer of j ≧ 0, R ¹ and R ³ are hydrogen or an organic group, R ² Are organic groups, but R ³ may be different groups, and when there are a plurality of R ¹ , they may be different groups and when there are a plurality of R ² , they may be different groups. However, the alkoxysilane represented by two general formulas are those good at least vapor pressure of the high-order silane vapor pressure is mixed or contacted.

For example, as shown in FIG. 1, when tetrasilane is used, dimethyldimethoxysilane is used, when normal pentasilane is used, tetramethoxysilane (TMOS) is used, and when normal hexasilane is used, tetramethylsilane is used. It is preferable to use ethoxysilane (TEOS).

The alkoxysiloxane used in the present invention has the general formula ( R ² O ) _3-x R ¹ _x Si (Si _y R ^{3 2} _y ) O (S
It is represented by i _z R ³ _2z ) SiR ¹ _w (OR ² ) _3-w . In the general formula, w and an integer of 0 to 3 (where w and x
Are not 3 at the same time), y and z are y and an integer of z ≧ 0, R ¹ and R ³ are hydrogen or an organic group, R ² is an organic group, but R ³ may be different groups. ^When there are a plurality of ¹ 's, they may be different groups, and when there are a plurality of R ² 's, they may be different groups. The Arukokishishiro key Sun, it is desirable that the vapor pressure is above the vapor pressure of higher order silanes are mixed or contacted. For example, when normal hexasilane is used as the higher order silane, the alkoxysilosan is 1,1,3,3-
It is advisable to use tetramethyl-1,3-diethoxydisiloxane.

When forming silicon particles according to the present invention, first, a mixed solution of a high-order silane and an alkoxysilane or an alkoxysiloxane is applied to the surface of a substrate in an inert gas atmosphere. At this time, the higher order silane and the alkoxysilane or the alkoxysiloxane may be mixed in advance, but may be mixed in the introduction pipe or on the substrate. Alternatively, the high-order silane (or alkoxysilane or alkoxysiloxane) may be first applied to the substrate, and then the alkoxysilane or alkoxysiloxane (or higher-order silane) may be applied.

The high-order silane, alkoxysilane, or alkoxysiloxane can be applied on the substrate by spin coating, dip coating, spray coating, bar coating, or curtain coating.
In the case of the spin coating method which is generally used, the rotation number of the spinner is generally 100 to 10,000 rpm, preferably 300 to 6000 rpm.

Next, the coating liquid is pressurized, preferably, a pressure of 50 kPa or more is applied to form silicon particles in the liquid. The silicon particles obtained at this time have extremely uniform particle diameters.

When forming a silicon film according to the present invention, first, silicon particles are formed from a part of the raw material in the raw material liquid, and then the silicon film is formed from the remaining raw material with the silicon particles as nuclei.

To form a silicon film, first, silicon particles are formed in a liquid by the above method, and then the substrate is heated to a temperature not lower than the boiling point of the alkoxysilane or alkoxysiloxane and not higher than the boiling point of the higher order silane at that pressure. To raise
Evaporate the alkoxysilane or alkoxysiloxane. For example, from FIG. 1, normal pentasilane and TMOS
It can be seen that it is necessary to raise the temperature to 130 ° C. in order to evaporate under 100 kPa.

Next, by a method such as photopolymerization by irradiation with ultraviolet light or thermal polymerization by heating, a predetermined silicon film is obtained from the unreacted higher silane remaining when the silicon particles are produced. At this time, the silicon particles formed by pressurization act as nuclei to induce crystal growth, so that the film can be formed at a lower temperature and a higher speed than in the past. That is, poly-Si can be obtained by setting the substrate temperature to about 450 ° C. or higher, preferably 500 ° C. or higher. At lower temperatures a
-Si is formed. The thickness of the obtained silicon film can be freely selected from about 5 nm to 50 μm by selecting the coating method.

Further, when forming a film at a high temperature, the temperature can be raised, especially reduced to about 0.001 to 1 kPa, and atomic hydrogen can be supplied to accelerate the polymerization and improve the film quality. Atomic hydrogen can be generated by any one of microwave discharge to hydrogen gas, irradiation of hydrogen gas with ultraviolet rays, and contact between hydrogen gas and a heated metal surface.

[0036]

EXAMPLES Each example of the present invention will be specifically described below. Regarding the physical properties of the silicon film formed in each example, the film thickness, photoconductivity (AM1.5, 100 mW / cm ² irradiation), dark conductivity, and optical gap were measured, and the measurement results were It is summarized in Table 2.

[0037]

[Table 2]

<Example 1> The apparatus shown in FIG. 2 was used as an experimental apparatus. A high-order silane dropping line 3, an alkoxysilane dropping line 4, and an exhaust line 6 are connected to the coating chamber 1, and a spin coater 8 is installed in the coating chamber 1. Further, in the film forming chamber 2, a gas supply line 5 and
An exhaust line 6 is connected, and a heater 7 is installed in the film forming chamber 2. The coating chamber 1 and the film forming chamber 2 are connected via a gate valve 14. Normal pentasilane was used as the liquid high-order silane, and TMOS was used as the alkoxysilane, and the film formation was performed by the following procedure.

First, with the gate valve 14 opened, the coating chamber 1 and the film forming chamber 2 are evacuated to 2 × 10 ⁻⁴ Pa,
After introducing helium gas up to 10 kPa from the gas supply line 5, 0.5 cm ³ of pentasilane was dropped onto the glass substrate 9 from the high-order silane dropping line 3 and applied using the spin coater 8.

Next, from the alkoxysilane introduction line 4 to T
0.5 cm ^{3 of} MOS on the previously coated pentasilane
After dropping and coating using the spin coater 8, helium gas was introduced again from the gas supply line 5 and pressure was applied until the pressure became 1 MPa. Next, the helium gas in the coating chamber 1 and the film forming chamber 2 was exhausted to 0.01 kPa from the exhaust line 6, and the remaining TMOS and the remaining normal pentasilane were evaporated. After that, when the substrate 9 was observed, silicon particles were formed.

Example 2 In Example 2, silicon particles were produced in the same manner as in Example 1 except that isopentasilane (i-Si ₅ H ₁₂ ) was used as the higher order silane. After evaporation of the remaining TMOS and the remaining isopentasilane, silicon particles were formed on the substrate.

Example 3 In Example 3, silicon particles were produced in the same manner as in Example 1 except that cyclopentasilane was used as the higher order silane and dimethyldimethoxysilane was used as the alkoxysilane. After evaporation of the remaining cyclopentasilane and the remaining dimethyldimethoxysilane, silicon particles were formed on the substrate.

Example 4 In Example 4, 1,1,3,3-tetramethyl-1,3-as an alkoxysiloxane instead of normal hexasilane or alkoxysilane was used.
Silicon particles were produced in the same manner as in Example 1 except that diethoxydisiloxane was used. After evaporation of the remaining normal hexasilane and the remaining 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, silicon particles were formed on the substrate.

Example 5 In Example 5, after forming silicon particles on the substrate 9 in the same manner as in Example 1, only the remaining TMOS is evaporated and then heated to form a silicon film on the substrate 9. Formed. That is, the procedure was as follows.

As the experimental device, the device used in Example 1 (shown in FIG. 2) was used. Normal pentasilane as liquid high order silane and TMO as alkoxysilane
A film was formed by using S in the following procedure.

First, with the gate valve 14 open, the coating chamber 1 and the film forming chamber 2 are evacuated to 2 × 10 ⁻⁴ Pa,
After introducing helium gas up to 10 kPa from the gas supply line 5, 0.5 cm ³ of pentasilane was dropped onto the glass substrate 9 from the high-order silane dropping line 3 and applied using the spin coater 8. Next, from the alkoxysilane introduction line 4, a TMOS was formed on the previously coated pentasilane in an amount of 0.
5 cm ^{3 was} dropped, and after coating using the spin coater 8, helium gas was introduced again from the gas supply line 5 to 1 MPa.
Pressurized until. Next, the helium gas in the coating chamber 1 and the film forming chamber 2 is exhausted to 100 kPa from the exhaust line 6, the substrate 9 is moved onto the heater 7, and the gate valve 1
4 closed.

Then, the substrate 9 was heated to 130 ° C. to evaporate the remaining TMOS. After TMOS evaporation, a liquid thought to be normal pentasilane containing particles thought to be silicon remained on the substrate 9. After that, helium gas was introduced from the gas supply line 5 at 500 cm ³ / min, the temperature of the substrate 9 was raised to 500 ° C. at 100 ° C./min while keeping the pressure in the film forming chamber 2 at 100 kPa, and then the substrate temperature was kept for 60 minutes. While holding, a silicon film was formed on the substrate 9.

Example 6 In Example 6, the substrate temperature in Example 5 was raised to 200 ° C. at 100 ° C./min, and the temperature was raised to 20 ° C.
A film was formed by heating for a minute.

<Example 7> In Example 7, a film was formed in the same manner as in Example 5 except that isopentasilane (i-Si ₅ H ₁₂ ) was used as the higher order silane.

<Example 8> In Example 8, except that cyclopentasilane was used as the higher order silane, dimethyldimethoxysilane was used as the alkoxysilane, and the evaporation temperature of the remaining dimethyldimethoxysilane was 100 ° C.
A film was formed in the same manner as in.

Example 9 In Example 9, normal hexasilane is used as the higher order silane, and 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane is used as the alkoxysiloxane instead of the alkoxysilane. Then, a film was formed in the same manner as in Example 5 except that the evaporation temperature of the remaining 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane was set to 180 ° C.

<Example 10> In Example 10, the apparatus shown in FIG. 3 was used as an experimental apparatus. The difference between the experimental apparatus of FIG. 3 and the experimental apparatus of FIG. 2 is that the experimental apparatus of FIG. 3 includes a low pressure mercury lamp 10 on the ceiling of the film forming chamber 2. After evaporating the remaining TMOS under the same conditions as in Example 5,
Film formation was performed by irradiating light with a wavelength of 400 nm or less using the low-pressure mercury lamp 10.

Example 11 In Example 11, the device shown in FIG. 4 was used as an experimental device. The difference between the experimental apparatus of FIG. 4 and the experimental apparatus of FIG. 2 is that the experimental apparatus of FIG. 4 has a microwave generation chamber 11 at the ceiling of the film forming chamber 2 and the hydrogen gas introduced from the hydrogen gas inlet 12 is It is introduced into the film formation chamber 2 as atomic hydrogen by the microwave generation chamber 11.

Under the same conditions as in Example 5, the remaining TMO
When the temperature was raised after S evaporation, the pressure was reduced to 0.1 kPa, and atomic hydrogen generated in the microwave generation chamber 11 was supplied onto the substrate 9 to form a film.

<Example 12> In Example 12, the apparatus shown in FIG. 5 was used as an experimental apparatus. The difference between the experimental device of FIG. 5 and the experimental device of FIG. 2 is that the experimental device of FIG. 5 has a spray gun 13 in the dropping line to the coating chamber 1. Under the same conditions as in Example 5, a spray gun 13 was used to apply a film by spray coating to form a film.

Comparative Example 1 In Comparative Example 1, film formation was performed under the same conditions as in Example 5 without using TMOS. Specifically, with the gate valve 14 opened, the coating chamber 1 and the film forming chamber 2 were evacuated to 2 × 10 ⁻⁴ Pa, and helium gas was introduced from the gas supply line 5 to 10 kPa, 0.5 cm ³ of pentasilane was dropped onto the glass substrate 9 from the silane dropping line 3 and applied using a spin coater 8.

Next, the substrate 9 was moved onto the heater 7, the gate valve 14 was closed, and then helium gas was introduced from the gas supply line 5 at 500 cm ³ / min to maintain the pressure in the film forming chamber 2 at 100 kPa. While the substrate 9 is 100 ° C.
The temperature was raised to 500 ° C. and the substrate temperature was maintained for 60 minutes to form a silicon film on the substrate 9.

Comparative Example 2 In Comparative Example 2, the substrate temperature was raised from 100 ° C./min to 200 ° C. under the same conditions as in Comparative Example 1 and the film was formed by heating for 20 minutes.

[0059]

The method for producing silicon particles according to the present invention is configured as described above. Therefore, according to claim 1,
It is possible to obtain silicon particles that are simpler and have a lower temperature than conventional ones and have excellent particle properties.

Further , since the high-order silane is not a gas at room temperature, the risk of explosion is reduced and the handling becomes easy. According to the second aspect , since the alkoxysilane or the alkoxysilosan becomes a liquid at room temperature, it becomes easy to mix or contact with the liquid high-order silane.

According to the third aspect , only the alkoxysilane or the alkoxysilosan can be evaporated.

Further, since the method for forming a silicon film of the present invention is configured as described above, according to claim 4 , a silicon film having characteristics that can be used as a device can be easily manufactured at a lower temperature and a higher speed than conventional ones. Can be manufactured. Therefore, it can be formed on an inexpensive glass substrate or a flexible polymer film, the cost of the device can be reduced, and the range of application is expanded. Moreover, since the raw material of the silicon particles to be the crystal nuclei can be used also in the formation of the silicon film, it becomes possible to form the silicon particles and the silicon film by supplying the raw material once, which simplifies the process. it can. From this point as well, the cost of the device can be reduced.

According to the fifth aspect , the high-order silane can be surely decomposed to form the silicon film.

According to claim 6 , by atomic hydrogen,
Polymerization of higher order silane can be promoted and the quality of the generated silicon film can be improved.

[Brief description of drawings]

FIG. 1 is a vapor pressure curve of higher order silane and alkoxysilane used in the present invention.

FIG. 2 is a cross-sectional view of an experimental apparatus used in Examples 1 and 5 of the present invention.

FIG. 3 is a transverse sectional view of an experimental device used in Example 10 of the present invention.

FIG. 4 is a transverse sectional view of an experimental apparatus used in Example 11 of the present invention.

FIG. 5 is a transverse sectional view of an experimental device used in Example 12 of the present invention.

[Explanation of symbols]

1 Coating Room 2 Film Forming Room 3 Higher Silane Drop Line 4 Alkoxysilane or Alkoxysiloxane Drop Line 5 Gas Supply Line 6 Exhaust Line 7 Heater 8 Spin Coater 9 Glass Substrate 10 Mercury Lamp 11 Microwave Generation Chamber 12 Hydrogen Gas Inlet port 13 Spray gun 14 Gate valve

Claims (6)

(57) [Claims] 1. The general formula Si _n H _{2n + 2} or Si _n H _2n (n
Is an integer of n ≧ 4) and the liquid high-order silane is mixed with or brought into contact with the liquid alkoxysilane or liquid alkoxysiloxane, and then pressurized to obtain silicon particles. Method for producing particles. 2. The alkoxysilane has the general formula SiR
¹ _m (OR ² ) _4-m , (where m is an integer of 0 to 3, R ¹ is hydrogen or an organic group, R ² is an organic group, but when m ≧ 2, a plurality of R ^1's are different from each other. Or a plurality of R ^{2 s} may be different groups when m ≦ 2)
Or represented by the general formula (R ⁴ O) _3-k R ³ _k Si
(Si _j R ⁵ _2j ) SiR ³ _h (OR ⁴ ) _3-h , {note that h, k
= 0 to 3 (however, h and k cannot be 3 at the same time), j is an integer of j ≧ 0, R ³ and R ⁵ are hydrogen or an organic group, R ⁴ is an organic group, and R ⁵ is different from each other. Or a plurality of R ³ may be different groups, and a plurality of R ⁴ may be different groups}. (R ⁷ O) _3-x R ⁶ _x
Si (Si _y R ^{8 2} _y ) O (Si _z R ⁸ _{2 z} ) SiR ⁶ _w (O
R ⁷ ) _3-w , {where w, an integer of 0 to 3 (however, w, x
Are not 3 at the same time), y and z are y, an integer of z ≧ 0, R ⁶ and R ⁸ are hydrogen or an organic group, R ⁷ is an organic group, and R ⁸ may be different groups. ^When there are a plurality of ⁶ 's, they may be different groups, and when there are a plurality of R ⁷ 's, they may be different groups.] Of the silicon particle according to claim 1. Production method. Wherein said alkoxysilane or manufacturing method of the silicon particles of claim 1, the vapor pressure of the alkoxy siloxane, characterized in that at least the vapor pressure of the higher silane. 4. After producing silicon particles by the method according to claim 3 , the remaining alkoxysilane or alkoxysiloxane is evaporated, and the remaining high-order silane is decomposed. A method for forming a silicon film, which comprises forming a silicon film. 5. The method for forming a silicon film according to claim 4 , wherein the decomposition of the remaining high-order silane is performed by raising the temperature to a predetermined temperature or irradiating with ultraviolet rays. 6. The method for forming a silicon film according to claim 4 , wherein the residual higher silane is decomposed in the presence of atomic hydrogen.