JPS60249315A - Deposited film forming method - Google Patents

Abstract

PURPOSE:To form a deposited film containing silicon atoms at a high film-forming rate with energy level reduced, while keeping high quality, by forming a gas atmosphere of hydrogen, specific chain silicon halide compound and compound of a III-family or V-family element in a deposition chamber, and by feeding heat energy. CONSTITUTION:A gas atmosphere of hydrogen, chain silicon halide compound expressed by a general expression SinX2n+2 [where, (x) stands for halogen atoms and (n) an integer of 1-6] and compound containing a III-family or V-family element is formed in a deposition chamber 1 in which a substrate 2 is arrayed, and by feeding heat energy to these compounds, a deposited film containing silicon doped with the said element is formed on the substrate 2. Feeding heat energy to the said gas is done by using, for example Joule heat generating device 4 and high frequency heating means, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a deposited film containing doped silicon;
In particular, the present invention relates to a method suitable for forming a deposited film of doped amorphous silicon (hereinafter referred to as a-3i) or polycrystalline silicon useful as a photoconductive film, a semiconductor film, etc.

[Prior art]

Conventionally, as a method for forming a-3i deposition 11, SiH
A glow discharge deposition method and a thermal energy deposition method using 4 or S i 2H6 as a raw material are known. That is,
These deposition methods use SiH4 or S as raw material waste.
This is a method in which i2H6 is decomposed using electrical energy or thermal energy (excitation energy) to form a deposited film of a-31 on a support, and the deposited film formed is a photoconductive film,
It is used for various purposes as a semiconductor or insulating film.

However, in the glow discharge deposition method, in which the deposited film is formed under high-power discharge, it is difficult to control reproducible and stable conditions such as not always being able to obtain a uniform discharge distribution state, and furthermore, it is difficult to control stable conditions with reproducibility. High-power discharge has a large effect on the film during formation, making it difficult to ensure the uniformity of electrical and optical properties and quality stability of the formed film, resulting in disturbance of the film surface during deposition and damage to the deposited film. internal defects are likely to occur. Especially l! 7-
It was extremely difficult to form a uniform film with electrical and optical properties of 1.1 in the electrical and optical properties using this method.On the other hand, even in thermal energy deposition, it is usually
Since a high temperature of C or higher is required, the support material that can be used is limited, and in addition, the probability that useful bonded hydrogen atoms in the desired a-5i will be eliminated increases, so it is difficult to obtain the desired properties. Or difficult l/h.

Therefore, one way to solve these problems is to
A-3i low heat energy deposition method (thermal CVD) using silicon compounds other than SiH4 and Si2H6 as raw materials
is attracting attention.

This low-heat thermal energy deposition method uses low-temperature heating instead of the glow discharge and high-temperature heating in the above-mentioned methods as excitation energy, and can produce the deposited film of a-3i with low energy. It is intended to enable implementation at the same level. In addition, the lower the temperature, the easier it is to uniformly heat the raw material gas, making it possible to produce high-quality products that maintain uniformity with lower energy consumption than the aforementioned deposition method. It is easy to control the conditions, stable and highly reproducible, and there is also the advantage that there is no need to heat the support to a high temperature, and that the selectivity of the support is widened.

[Purpose of the invention]

The present invention has been made in view of the above points, and uses low-level thermal energy as excitation energy to form a deposited film containing silicon atoms at a high deposition rate of 1 while maintaining high quality at a low energy level. It is an object of the present invention to provide a thermal energy Lm product method that can form a thermal energy Lm product.

Another object of the present invention is to form a high-quality deposited film that ensures uniformity of electrical and optical properties and stable quality even in the formation of a large-area, thick deposited film. The goal is to provide a method that can be used.

[Summary of the invention]

For the above purpose, the general formula: 5inX
2n+2 (wherein, Forming a gaseous atmosphere of hydrogen, using thermal energy, excite and decompose the compound and hydrogen, and the substrate contains silicon doped with an impurity element. This is achieved by a method for forming a deposited film, which is characterized by forming a deposited film.

In the method of the present invention, a silicon compound is used as a raw material for supplying Si, and a compound containing these atoms is used for introducing atoms belonging to Group 1 or Group V of the periodic table. The deposited film formed is a deposited film containing silicon atoms and atoms belonging to Group M or Group V of the periodic law, and can be used for various purposes as a functional film such as a photoconductive film or a semiconductor film. It is something.

The chain halogenated silicon compound of the above general formula is a linear or branched chain silicon hydride compound (chain silane compound).
It is a tetrahalogen derivative of 5inH2n+2, and is a compound that is easy to manufacture and has high stability. In the general formula,
X represents a halogen atom selected from chlorine, chlorine, bromine and iodine. The value of n is limited to 1 to 6 because n
This is because the larger the value, the easier it is to decompose, but the more difficult it is to vaporize, the more difficult it is to synthesize, and the lower the decomposition efficiency is.

Preferred examples of the chain halogenated silicon compound of the general formula include the following compounds.

(1) S i F 4 , (2) S i 2 F
e.

(3) Si3FB, (4) si4FxO.

(5) S i 5F12. (e) Si6F14゜(7
) S i C14, (8) S i 2 Cl 6
.

(8) si, cte, (10) SiBr4゜(11
) S i 2 B r 6 , (12) S i 3
B r8.

(13) S i I 4゜In the deposited film formed in the method of the present invention, for example, B,
Group II of the periodic table such as AI, Ga, In, T1, etc. or N
, P, As, Sb, Bt, etc., are used as raw materials to introduce atoms belonging to Group V such as P, As, Sb, Bt, etc. Compounds containing If atoms and easily excited and decomposed by thermal energy are used. Such compounds include, for example,
PH3, P2H4, PF3, PF5.

PCl3. AsH3, AsF3. AsF5゜AsCl3
．． SbH3, SbF5. BiH3°BF3. BCl3.
BBr3. B2H6゜B4H10, B5H9, B6H1
It is possible to hang 0,B6H12゜AlCl3, etc.

In the method of the present invention, a gaseous silicon compound such as those listed in 1) and a compound containing an atom belonging to group V of the periodic table are introduced into the deposition chamber. Thermal energy is given to the compounds, which excite them,
It is decomposed, and a deposited film (a-3i film) containing silicon atoms and atoms belonging to Group V of the periodic table is formed on a support placed in the deposition chamber.

In the present invention, hydrogen radicals generated during the excitation/decomposition reaction are removed by forming a gaseous atmosphere of a chain silicon halide compound of the general formula, a compound containing an impurity element, and hydrogen in the chamber. Increase the efficiency of the reaction. Second, hydrogen is incorporated into the deposited film that is formed, which plays a role in reducing defects in the Si bond structure.

In addition, in the process of 1 decomposition, the chain halogenated silicon compound of the above general formula becomes SiX, 5iX2, 5i2X3.5i2X4
．． 5i2X5. Si, 3X3.

5i3X4, 5i3X5, 5iaXs, Si3X7. By generating Natono Cal, and by hydrogen,
Radicals in which St, X and H are combined are generated, so through a reaction process involving these radicals, finally
A high-quality film with a low localized density in which the St tangling pond is sufficiently terminated with H or X can be obtained.

Further, the chain halogenated silicon compound of the general formula is 2
Although more than one type of these compounds may be used in combination, in this case, properties that are equivalent to the average of the film properties expected by each compound, or properties that are synergistically improved can be obtained.

Next, imparting thermal energy to the silicon compound gas introduced into the deposition chamber includes a Joule heat generating element;
This is carried out using high frequency heating means or the like.

Examples of the Joule heat generating element include heaters such as heating wires and heating plates, and examples of the high frequency heating means include induction heating and dielectric heating.

To describe an embodiment using a Joule heat generating element, a heater is placed in contact with or close to the back surface of the support to conductively heat the surface of the support, thermally excite and thermally decompose the raw material gas near the surface, and transfer the decomposition products to the support. Deposit on the surface. Alternatively, it is also possible to place the heater near the surface of the support.

Hereinafter, the method of the present invention will be explained in detail with reference to FIG.

FIG. 1 is a schematic diagram of a deposited film forming apparatus for forming a functional film such as a photoconductive film, a semiconductor film, or an insulating film made of a-3T on a support.

Formation of the deposited film takes place inside the deposition chamber l.

Reference numeral 3 placed inside the deposition chamber 1 is a support base on which a support is placed.

Reference numeral 4 denotes a heater for heating the support, and power is supplied to the heater 4 through a conductive wire 5. The inside of the gas introduction pipe for introducing the raw material gas of a-3i and gases such as carrier gas used as needed into the deposition chamber 1 is connected to the deposition chamber 1.

The other end of this gas introduction pipe 17 is connected to a gas supply source 9゜10.11.12 for supplying raw material gas for a-3i formation and gases such as carrier gas used as necessary. . From the gas supply sources 9, 10, 11.12 to the deposition chamber l
To measure each gas meteor flowing towards the corresponding flow meter 15-1.15-2.15-3.1
Branched gas introduction pipe 17-1.17- corresponding to 5-4
It is provided in the middle of 2.17-3.17-4. Valve 14-1.14-2.14 before and after each flow meter.
-3.14-4.16-1.16-2.16-3.16
-4 are provided, and by adjusting these/helps, a predetermined flow rate of waste can be supplied. 13-1. ．． 13
-2.13-3. i:3-4 is a pressure meter, which is used to measure the high pressure (till pressure) of the corresponding flow meter.

The gases passing through the flow meters are mixed and introduced into a certain deposition chamber 1 under reduced pressure by an exhaust device (not shown). In addition, the pressure meter 18 measures the total pressure in the case of mixed gas.

A gas exhaust pipe 20 is connected to the deposition chamber 1 in order to reduce the pressure inside the deposition chamber 1 and to exhaust the introduced gas. The other end of the gas exhaust pipe is connected to an exhaust device (not shown).

In the invention, the number of gas supply sources 9, 10, 11, 12 can be increased or decreased as appropriate.

In other words, when a single raw material gas is used, one waste supply source is sufficient. However, when using a mixture of two types of raw material gas, or when mixing a single raw material gas (catalyst gas, gear 9 arc, etc.), two or more are required.

Note that some raw materials remain in liquid form and become gas at room temperature, so if the raw materials are liquid, a vaporizer (not shown) is installed. There are two types of vaporizers: those that utilize heating and boiling, and those that allow carrier gas to pass through the liquid original-1. The raw material residue obtained by vaporization is introduced into the deposition chamber 1 through a flow meter.

A typical PI using the apparatus shown in FIG.
The a-3i deposited film forming method of the present invention will be explained in more detail using an example of a method for forming an N-type diode device.

FIG. 2 is a schematic cross-sectional view for explaining the configuration of a typical PIN diode device obtained by the present invention.

21 is a support, 22 and 26 are thin film electrodes, 23 is a P-type a-81 layer, 24 is an I-type cy) a-Si layer, 25 is an N-type cy) a-Si layer, 27 is a semiconductor layer, 28 is a conducting wire. The support 21 is semiconductive, preferably electrically insulating. The semiconducting support is eg Si.

Examples include a plate made of a semiconductor such as Ge.

Polyester is used as an electrically insulating support.

Films or sheets of synthetic resins such as polyethylene, polycarbonate, cellulose acetate, polypropyrolene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used.

In particular, in the method of the present invention, the temperature of the support is 150°C.
Since the temperature can be relatively low at around 300°C, it is possible to use materials with low heat resistance that cannot be applied to conventional glow discharge deposition methods or thermal energy deposition methods among the materials that form the above-mentioned supports. It is now possible to use other supports.

The thin film electrode 22 is made of, for example, NiCr, Al, or Cr.

Mo, Au, Ir, Nb, Ta, V, Ti.

Pt, Pd, In2O3, 5n02. ITO(I n2
03 +S, n02) or the like on a support using a method such as vacuum evaporation, electron beam evaporation, or sputtering.

The thickness of the electrode 22 is desirably 30 to 5×10 4 , more preferably 100 to 5×10 3 .

In order to make a predetermined layer among the layers constituting the semiconductor layer 27 of a-3i N-type or P-type as desired, an N-type impurity or a P-type impurity is formed during layer formation. It is sufficient to dope the material into the layer while controlling its concentration.

P-type impurities doped into the semiconductor layer include atoms belonging to Group Ⅰ of the periodic table, especially, for example, B and A.
Preferred examples include I, Ga, In, T1, etc., and N-type impurities include atoms belonging to Group V of the periodic table,
Among them, N, P, As, Sb, Bi, etc. are preferred, and B, Ga, P, Sb, etc. are particularly suitable.

In the invention, the amount of impurity doped into the semiconductor layer 27 in order to impart a desired conductivity type is determined as appropriate depending on the desired electrical and optical characteristics, but according to the periodic law. In the case of impurities in group Ⅰ of the table, 3 X I O'~4a
t om i (doping should be done within the range of 5XlO
Doping may be done in a range of -3 to 2 atomic%.

In order to dope the above-mentioned impurity into a predetermined layer of the layers constituting the semiconductor layer 27, a raw material for impurity introduction may be introduced in a gaseous state into the storage chamber 1 during layer formation. The raw materials for introducing such impurities include those in a gaseous state at room temperature and pressure, or at least under layer-forming conditions;
Alternatively, a material that can be easily turned into scum by a vaporizer is used.

Specifically, raw materials (impurity gas) for introducing such impurities include PH3 and P2 for introducing N-type impurities.
H4, PF3, PFs.

PCl3, AsH3, AsF3, AsF5゜AsC
l3, SbH3, SbF5. BiH3.

On the other hand, BF3 is used for introducing P-type impurities.

BCl3, BBr3, B2H6', B4H10
゜BsH9, BsHlo, BeHx2. Examples include AlCl 3 and the like.

Next, the method for forming the semiconductor layer 27 will be explained in more detail.

First, the supporting body 2 on which the thin film of the electrode 22 was previously installed
1 is placed on the north side of the support stand 3 in the deposition chamber 1, and the air in the deposition chamber is exhausted through the waste exhaust pipe 20 by an exhaust device (not shown) to reduce the pressure. The atmospheric pressure inside the deposition chamber under reduced pressure is 5X10-5T.
orr or less, preferably J Niha 10-GT or r or less.

Once the pressure inside the deposition chamber 1 has been reduced, the heater 4 is energized to heat the support 3 to a predetermined temperature. The temperature of the support at this time is 150 to 300°C, preferably 2oo to 2
It is assumed to be 5o0c.

As described above, since the support temperature is relatively low in the method of the present invention, glow discharge deposition method, SiH4, Si
Since there is no need to heat the support to high temperatures as in thermal energy deposition methods using 2H6 as raw material, the energy consumption required for this purpose can be saved.

Next, in order to stack a P-type a-5i layer on the thin layer electrode 22 on the support 21, the valve 14-1 of the supply source 9 is filled with the S1 supply raw material gas as listed above. .16
-1 and a valve 14-5, 16-5 of the supply source 29 filled with a halogen compound, and a valve 14-2 of the supply source lo stored with P-type impurity gas.

16-2 are opened, and a mixed gas containing a Si supply raw material gas and a P-type impurity gas mixed at a predetermined mixing ratio is introduced into the deposition chamber 1.
Send it inside.

At this time, the corresponding flow meter 15-1゜15-2.1
After measuring in 5-5, perform fAf and round adjustment. The flow rate of raw material waste is 10 to 110003 CC, preferably 20 to 500 CC.
A range of 5 CCM is desirable.

Ift, * of the P-type impurity gas is determined from the flow rate of the source gas x the doping concentration.

However, since the amount of impurity gas mixed is extremely small, in order to facilitate flow rate control, the impurity gas is usually diluted with H2 gas or the like to a predetermined degree and then stored and used.

The pressure of the mixed gas in the deposition chamber 1 is 10-2 to 100To
rr, preferably maintained in the range of 10-2-ITorr.

In this way, thermal energy is imparted to the raw material gas flowing near the surface of the support 2, promoting thermal excitation and thermal decomposition, and the generated substance a-3i and trace amounts of P-type impurity atoms are transferred to the support. deposited on top.

Decomposition products other than a-3i and P-type impurity atoms, undecomposed surplus raw material gas, etc. are discharged through the gas exhaust pipe 20, while new raw material gas is discharged through the gas introduction pipe 17.
A P-type a-3i layer 23 is formed. The layer thickness of P type a-3i is 100 to 10
It is desirable to have 4 people, preferably in the range of 300 to 2000 people.

Then the valve 14-1.1 connected to the gas supply 9.10
6-1.14-2.16-2 are all closed to stop the introduction of scum into the deposition chamber 1.

After removing the dregs from the deposition chamber by driving the exhaust device (not shown), the valves 14-1 and 1fl+-1 are opened again to introduce the raw material gas for supplying Si into the deposition chamber 1. In this case, the preferred flow conditions and pressure conditions are the P-type a-3i layer 23
The conditions are the same as those for the formation of .

In this way, the non-doped, i.e. type 1, a-3i layer 2
4 is formed.

The layer thickness of type 1 (1) a-Si layer is 500 to 5×1
04 people, preferably in the range of 1000 to 10,000 people.

Next, a gas supply source 11 in which N-type impurity gas is stored.
Open the valve 14-3.16-3 connected to the deposition chamber 1.
An N-type impurity gas is introduced into the chamber.

The flow rate of the N-type impurity gas is determined from the flow rate of the Si supply source gas multiplied by the doping concentration, similar to the meteor determination of the P-type impurity gas.

In the same way as when forming the P-type a-3i layer 23, thermal energy is applied to the raw material gas flowing near the surface of the support 2, promoting thermal excitation and thermal decomposition, and the decomposition product a-3i is transferred to the support. The N-type a-3i layer 25 is formed by being deposited on top and a trace amount of N-type impurity atoms of decomposition products mixed into the deposit.

The thickness of the N-type a-3i layer 25 is preferably in the range of 1.00 to 104 layers, preferably 300 to 2.000 layers.

In the formation of the P-type and N-type a-3i layers as described above, the raw material gas for supplying Si and the gas for introducing impurities used in the method of the present invention require thermal energy as described above. 5 to 50 people/s because it is easily excited and decomposed by
A layer formation rate as high as ec can be obtained.

Finally, a thin layer electrode 26 is formed on the N-type a-3i layer 25 using the same method as the thin layer electrode 22 to have the same layer thickness as the thin layer electrode 22, thereby completing a PIN type diode device. .

The PIN type diode device thus formed satisfied predetermined characteristics and quality.

According to the method of the present invention, in addition to forming the semiconductor layer of the PIN diode device described above, a single layer or multilayer a-3i layer having desired electrical and optical properties can be formed. can be formed. In addition, in the example explained above, the deposited layer was formed under reduced pressure, but
Without being limited thereto, the method of the present invention can be carried out under normal pressure or under increased pressure, if desired.

According to the method of the present invention as described above, thermal energy with a low amount of heat is used as excitation energy, and raw material waste that is easily excited and decomposed by the thermal energy is used. a- at level
It has become possible to form a 3i deposited layer, and it has become possible to form an a-3i deposited layer with excellent uniformity in electrical and optical properties and stability in quality. Therefore, in the method of the present invention, the conventional glow radiation deposition method and thermal energy 11
It is now possible to use a support made of a material with low heat resistance, which cannot be applied to the one-layer method, and it is also possible to save energy consumption required for heating the support at high temperatures.

Furthermore, although thermal energy is used as excitation energy, since it is applied with a low amount of heat rather than a high amount of heat, the energy can always be applied uniformly to the predetermined space occupied by the source gas to be applied, and therefore the deposited film is It is now possible to form 6-cutter uniformly with high precision.

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

Example 1 As the chain silicon halide compound of the general formula, the above exemplary compound (1), (2), (3), or (5) was used, and as a compound containing an impurity element, PH3 was B2H6. P was used as an impurity using the apparatus shown in Figure 1.
An a-5i deposited film doped with (N type) or B (P type) was formed.

First, conductive film substrate (manufactured by Corning, #705
9) on the support stand 2, and use the exhaust device to remove the deposition chamber 1.
Evacuate the inside and 10-[iT.

The pressure was reduced to rr. The support temperature was set at 220°C, and the silicon halide compound, which was in the form of a gas, and P
1l 103cc of gas mixed with H3 gas or B2H6 gas at a ratio of 1:5X10-3, 403cc of hydrogen gas
M was introduced into the deposition chamber at a flow rate of M, and the atmospheric pressure in the chamber was brought to 0. I
A doped a-3i film was formed by maintaining the temperature at T o r r. The film formation rate was 30 people/sec.

For comparison, a similarly doped a-5i film was formed using S i 2H6. Film deposition speed is 12 people/
It was sec.

Next, the obtained a-Sil+2 sample was placed in a vapor deposition tank,
A comb-shaped A-shaped gap electrode (
After forming a film (length 250 mm, width 5 mm), apply voltage 1.
Measure the dark current at 0V, calculate the dark conductivity σd, and calculate a-3i.
The results of two evaluations of the membrane are shown in Table 1.

From Table 1, it can be seen that the a-3i film according to the present invention has sufficient doping efficiency and high σd even at a low substrate temperature, compared to the case using conventional Si 2H6.

Example 2 The substrate was a polyimide substrate, the chain halogenated silicon compound of the general formula was used, and the exemplified compounds (12), (1
3) Same as Example 1 except that (15) was used.
-5i film was formed and σd was determined. The results are shown in Table 2.

Example 3 The above-mentioned exemplified compounds (1), (2), (3), (5) are used as the linear halogenated silicon compounds of the above-mentioned general formula.
The PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG.

First, the glass plate 2 on which 1000 ITO films 22 were deposited
1 was placed on a support stand, and a B-doped P-type film-5i film 24 (film thickness: 400 layers) was formed in the same manner as in Example 1. Note that the support temperature was set at 220°C.

Next, the introduction of B2H6 gas was stopped and the pressure inside the deposition chamber was reduced to 0.
I-type film - SiHfi25 (film thickness: 5000 mm) was prepared using the same method as in the case of P-type film-3i11 except that the Torr was set at 5 Torr.
was formed.

Then, N doped with P in the same way as in Example 1
A type film-3i film 26 (film thickness: 400 mm) was formed. Note that the light irradiation conditions were the same as those for the P type. Further, an An electrode 27 having a thickness of 100 mm was formed on this N-type film by vacuum evaporation to obtain a PIN-type diode.

For comparison, s 12H8 was used in the same manner as PI
An N-type diode was formed.

The thus obtained guioto'element (area 1 cm2)
The 1-v characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3←From Table 3, conventional Si
Compared to the case using 2H6, the deposited film according to the invention provides excellent rectification properties even at low substrate temperatures.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
At light irradiation intensity AMI (approximately 100 mW/cm2),
Conversion efficiency 6.9%, open end 0.7 V, short circuit current 10 m
A/cm2 was obtained.

Example 4 Transparent conductive film (polyester base) as a substrate
, PIN was produced in the same manner as in Example 3, except that the exemplary compounds (6), (7), and (9) were used as the linear silicon halide crude compound of the general formula, and the support temperature was set at 250°C. A type diode was fabricated, and the rectification ratio and η value were determined. The results are shown in Table 4.

Table 4 [Effects of the Invention] According to the present invention, a high quality silicon deposited film can be formed at a low substrate temperature and at a high film formation rate. Moreover, when the film to be formed is wide area and thick,
However, uniform electrical and optical characteristics can be obtained, and quality stability can also be ensured, which is an unprecedented effect.

In addition, it saves energy because it does not require high-temperature heating of the substrate, it can form a film even on substrates with poor heat resistance, the process can be shortened by low-temperature treatment, and the raw material compound can be easily synthesized. It is inexpensive, has excellent stability, and has the advantage of being less dangerous in handling.

[Brief explanation of drawings]

3: Support stand 4: Heater 5: Conductor 6-1.6-2.6-3: Gas flow 9, 10.11.12: Gas supply source 13-1.13-2.3 to 3.13- 4.18: Pressure meter 14-1.14-2.14-3.14-4゜16
-1.16-2.16-3.16-4,21: Valve 15-1.15-2.15-3.15-4: Flow meter 17.17-1.17-2.17-3. 17-4:
Gas introduction tube - one nose 2o: Gas inlet trachea 22.26: fiJ membrane electrode 23: P type a-3i layer 24
: I-type a-3i layer 25: N-type a-3i layer 27: Semiconductor layer 28: Conductor applicant: Gyanon Co., Ltd.

Claims (1)

[Scope of Claims] (Inside the chamber housing the body, a chain halogenated silicon compound represented by the general formula: 5inX2n+2 (wherein, X is a halogen atom and n is an integer from 1 to 6); A gaseous atmosphere of hydrogen and a compound containing an element belonging to Group I or V of the Periodic Table is formed, thermal energy is applied to these compounds, and silicon doped with the element is formed on the substrate. A method for forming a deposited film characterized by forming a deposited film that collapses.