JPS6188514A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To obtain a homogeneous deposited film by individually introducing active seeds which are generated by decomposition of compound including Si and halogen and film forming materials and exciting and reacting film forming materials with discharge energy. CONSTITUTION:Gas such as SiF4, Si6H14 or compound of a material which assures easy gasification is heated 113 to form active seeds such as SiF2*. These active seeds are introduced 116 into a film forming chamber and moreover a kind or two or more kinds of film forming materials such as SiH4, SiHF3, etc. are also introduced 116 individually thereto. An introducing flow rate ratio of material gas and active seeds is set to 8/2-4/6 and it is selected in accordance with depositing condition and kinds of active seeds. The film forming material is excited by generating 117 the discharge energy to realize reaction with active seeds and thereby a-Si film is formed on a substrate 103. Moreover, an impurity element of gas condition or a compound including it can be doped to the deposited film under the normal temperature and pressure condition. This method realizes homogeneous deposited film with good reproducibility.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to silicon-containing deposits +1A, especially amorphous silicon or polysilicon for use in functional films, especially semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, etc. The present invention relates to a method suitable for forming a deposited film of crystalline silicon.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion plating, photo CVTL, etc., and plasma CVD is generally used. Widely used and commercialized.

Deposited II materials made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity and mass production, including uniformity and reproducibility. , there is room for further improvement of comprehensive characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, and the deposited film that is formed is often affected by S significantly. Moreover, device-specific parameters must be selected for each device.
Therefore, the reality is that it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop an amorphous silicon film with electrical, optical, photoconductive, and mechanical properties that fully satisfy all requirements, it is currently best to form it by plasma CVD. It is said that

However, depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility using high-speed 115i deposition. Forming an amorphous silicon deposited film by this method requires a large investment in equipment for mass production, and the management items for mass production are also complicated.
The allowable management range has become narrower, and equipment adjustments have become more delicate, so these have been pointed out as problems that need to be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the drawbacks of the plasma CVD method described above and provides a new method for forming a deposited film that does not rely on conventional forming methods.

[Purpose and outline of the invention]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film quality uniform, while also being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The object of the present invention is to provide a method for forming a deposited film that can achieve the following.

The above purpose is to create a film that chemically interacts with active species generated by decomposing a compound containing silicon and halogen in a film formation space for forming a deposited film on a substrate. The present invention is characterized in that a deposition n-port is formed on the substrate by separately introducing raw material gases and applying discharge energy to them to excite the film-forming raw material gases and cause them to react. This is achieved by a deposited film formation method. [Embodiment] In the method of the present invention, discharge energy such as plasma is used as energy to excite the film-forming raw material gas and cause it to react, but since active species are introduced into the film-forming space as one of the raw materials, it is different from the conventional method. Film formation is possible even with a relatively low discharge energy, and the deposited film that is formed is extremely unlikely to be adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, according to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

Moreover, in the present invention, in addition to discharge energy, light energy and/or thermal energy can be used in combination, if desired. The light energy can be applied to the entire substrate using an appropriate optical system, or it can be applied to only desired parts in a selective and controlled manner.
The formation position, film thickness, etc. of the deposited film on the substrate can be easily controlled. Further, as the thermal energy, thermal energy converted from light energy can also be used.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. As a result, the deposition rate can be dramatically increased compared to the conventional CVD method, and in addition, it is possible to further reduce the substrate temperature during the formation of the J'1 film. Deposited films with stable film quality can be provided to a large extent commercially and at low cost.

In the present invention, the active species from the decomposition space introduced into the film forming space has a lifespan of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds or more from the viewpoint of productivity and ease of handling. A certain active species is selected and used as desired, and the active species constitutes the main component of the deposit formed in the film forming space. Also, Sei II! 2J
When the fX #4 gas is excited by discharge energy in the growth fl'J space and forms a deposited film, it is simultaneously introduced from the decomposition space and contains active species containing constituents that will become the main constituents of the deposited film to be formed. interact chemically; As a result, a desired deposited film can be easily formed on a desired substrate.

In the present invention, as the compound containing silicon and halogen introduced into the decomposition space, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, For example, Si Y
(u is an integer north of l, u 2u+2, Y is F, C1, Br, or engineering.) Chain silicon halide, Si Yv 2v (V is an integer of 3 or more and 2, Y is the meaning described above) ) is a cyclic silicon halide represented by 5iux+y=2u or 2u+2. ), and the like.

Specifically, for example, SiF4, (SiFz)s, (SiF
2) b, (SIF2) 4. S i2 F6, S4
3F[], SiHF3. SiH2F2.5iC14 (
SiC12)5,5iBr, , (SiBr2)s,S
Examples include those that are in a gaseous state or can be easily gasified, such as i2C16, 5i2C1, F3.

In order to generate active species, in addition to the above-mentioned compound containing silicon and /\logen, other silicon compounds such as simple silicon, hydrogen, and halogen compounds (for example, F2 gas, C12 gas, gasified Brz) may be used as necessary. , 12, etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in a decomposition space.

The film-forming raw material gas used in the method of the present invention includes hydrogen gas and/or a halogen compound (for example, F2 gas, C
12 gas, gasified Br2, 2 etc.) are advantageously used. In addition to these film-forming raw material gases, an inert gas such as argon or neon can also be used.

When using a plurality of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be individually supplied from independent sources and then introduced into the film forming space. It can also be introduced into

In the present invention, the ratio of the active species to the film-forming raw material gas in the film-forming space is determined depending on the deposition conditions, the type of active species, etc., and is preferably 10:1.
~1:10 (introduction flow j;.

The ratio) is appropriate, more preferably 8:2 to 4:6.

Further, it is possible to dope the deposited film formed by the present ffi IJIJ method with an impurity element. The impurity source used is, as a p-type impurity, an element of Group 1II A of the periodic table, such as B or AI.

Preferred examples include G a , I n , T I, etc., and examples of It-type impurities include those from Group ■ A of the periodic table.
Suitable elements include N, P, As, Sb, Bi, etc., particularly B, Ga, and P.

sb etc. are optimal. The impurity j- to be doped is appropriately determined depending on desired electrical and optical characteristics.

Compounds containing such impurity elements as components are those that are gaseous at normal pressure, or at least gaseous under deposited film forming conditions, and that can be easily vaporized using an appropriate vaporizer 6. Is it preferable to do so? Such compounds include PH, U, P, I-1,, PF,, P
F9. PC13, AsH,, AsF3. AsF3. As
C13, SbH3, SbF5. SiH3, BF3
, BCI3, BBr3, B2H6,B
4 H, , B 5 H9, B 5 H, □ , B, H
,. , B6 Hl 2 , A Ic 13 and the like. The compounds containing impurity elements may be used alone or in combination of two or more.

In order to introduce a compound containing an impurity element into the film forming space, it can be mixed with the film forming raw material gas etc. in advance, or it can be introduced individually from multiple independent gas supply sources. Next, the present invention will be described with reference to typical examples of electrophotographic imaging members formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining an example of the configuration of a typical photoconductive member obtained by the present invention.

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2 and a photosensitive layer 13.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, Steer L/S, A1. CrlMo.

Examples include gold 14 such as Au, Ir, Nb, Ta, ■, Ti, PL, and Pd, or alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface may be NiCr, A1. C
r, Mo, Au, I r, Nb, Ta, ■, Ti, Pt
, Pd, In203.5n02, I To (i n2
03 +S n02 ), or a synthetic resin film such as a polyester film, NiCr, A1. Ag, Pb,
Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta,
Vacuum evaporation, electron beam evaporation, etc. of metals such as V, Ti, and Pt.
The surface is made conductive by sputtering or by laminating with the metal. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired.
If the photoconductive member 10 shown in FIG. 81 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying.

For example, the intermediate layer 12 includes a photosensitive layer 13 from the support 11 side.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moves toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has the function of allowing easy passage.

This intermediate layer 12 is made of amorphous silicon 7 (hereinafter referred to as a) containing hydrogen atoms (H) and/or halogen atoms (X).
It is written as -3i(H,X). ), and contains, for example, a p-type impurity such as B or a p-type impurity such as P as a substance that controls electrical conductivity.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001 to 5×104 atomic ppm, more preferably 0.5 to IXIO4 atomic ppm, optimally 1 to 5×103103 atomic ppm.

When forming the intermediate layer 12, up to the formation of the photosensitive layer 13, I! l! It can be done continuously. In that case, the active species generated in the decomposition space, the film-forming raw material gas, and optionally an inert gas and a compound gas containing an impurity element as ingredients are used as raw materials for forming the intermediate layer. The intermediate layer 12 may be formed on the support 11 by introducing them separately into the film forming space where the support 11 is installed, and using a retired electrician's nel key.

The silicon- and halogen-containing impurities that are introduced into the decomposition space to generate active species when forming the intermediate layer 12 easily generate active species such as 5IF2 at high temperatures.

The thickness of the intermediate layer 12 is preferably 30A to 10μ, more preferably 40A to 8μ, and most preferably 50A to 5μ.

The photosensitive layer 13 has, for example, an A-3i (H,

The layer thickness of the photosensitive layer 13 is preferably 1 to 100
, more preferably from 1 to 80 l, most preferably from 2 to 50. It is desirable that this is done.

The photosensitive layer 13 is an i-type a-Si (H, Alternatively, a substance that controls conduction characteristics of the same polarity may be added to the actual 7. If there is a lot of H-, the amount is much less than the sample amount.
It may also be contained.

Similarly to the case of the intermediate layer 12, the photosensitive layer 13 is formed using a compound containing silicon and halogen in the decomposition space.
By decomposing these at high temperatures, active species are generated and introduced into the film forming space. Separately from this, an inert gas, a gas of a compound containing an impurity 'lk element as a component, etc. are added to the film forming space where the support 11 is installed, as necessary. The intermediate layer 12 may be formed on the support 11 by one person using discharge energy. FIG. 2 shows an a- FIG. 2 is a schematic diagram showing an example of a PIN type diode device type using a 5i deposited film.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type a-3i layer 24, an i-type (1) a
-S 4 layer 25 and p-type a-Si layer 26. 28 is a conducting wire.

The substrate 21 is semiconductive, preferably electrically insulating. Examples of semiconductive substrates include Si
, Ge, and other semiconductors. The thin film electrodes 22.27 include, for example, NiCr, A1. Cr, Mo, Au, r
r, Nb, Ta, V, Ti, Pt, Pd, In2O3,
S n02 , ITO (In203 +S n02 )
It can be obtained by forming a thin film such as the above on a substrate by vacuum evaporation, electron beam deposition, sputtering, or the like.

The film thickness of the electrode 22.27 is preferably 30 to 5X.
104A, more preferably 100 to 5×103A.

In order to make the film constituting the semiconductor layer 23 of a-5i n-type 24 or p-type 26 as necessary, an n-type impurity, a p-type impurity, or both impurities among the impurity elements are added during layer formation. The amount of doping is controlled in the layer to be formed (formed by observation).

To form n-type, i-type and p-type a-3i layers, according to the method of the present invention, a compound containing silicon and halogen is placed in the decomposition space, and by decomposing these at high temperature, For example, 1'j species are generated in SIF 2- and introduced into the film forming space. Separately, a gas for the formation material 9 and, if necessary, an inert gas and a compound gas containing an impurity element as a component are introduced into the film formation space where the support 11 body 11 is installed, It may be formed by using radiation energy. The thickness of the n-type and p-type a-Si layers is preferably in the range of 100 to 104 Å, more preferably in the range of 300 to 2000 Å.

Further, the thickness of the a-Si layer of i5 is preferably 5
00-104A, more preferably 1000-100OO
A range of A is desirable.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 3, i
Type, p type and n type a-5r combination is represented by shape 1.
child .

In FIG. 3, 101 is a deposition chamber, inside), (
body skin F, 'desired on one unit 102), (body 103?/t
&,':';.

It's dirty.

104 is a heater for heating the body, and the guide 105
Power is supplied through the device and generates heat. The substrate temperature is not particularly limited, but in carrying out the method of the present invention, it is preferably 50 to 150°C, more preferably 100 to 150°C.
It is desirable that

Reference numerals 106 to 109 indicate gas supply sources, which are provided depending on the number of gases of film forming raw materials, inert gases used as necessary, and compounds having impurity elements as components. When using liquid raw material compounds, an appropriate vaporization device is provided.

In the figure, the gas supply sources 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply sources 106 to 109. The valves marked with ``e'' are used to adjust each gas fRfa.

110 is a gas introduction pipe into the film forming space, and 111 is a gas pressure gauge.

In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is a solid Si particle, 115 is an introduction pipe for a compound containing gaseous silicon and halogen, which is a raw material for active species, and the decomposition space 11
The activated species generated in step 2 are introduced into the formation space 101 via the introduction pipe 116.

Reference numeral 117 denotes a discharge energy generating device, which includes a matching box 117a and a cathode electrode 117b for introducing high frequency.
Equipped with etc.

The discharge energy from the discharge energy generator 117 is applied to the raw material gas etc. flowing in the direction of the arrow 119, and a-5i is applied to the entire substrate 103 or a desired portion by a die which excites the gas etc. of the film forming raw material and causes a reaction. A deposited film is formed. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First, a polyethylene terephthalate film substrate 103
was placed on the support table 102, and the inside of the deposition space 101 was evacuated using an exhaust device.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, use the gas supply source 106 to supply 150 sccM of H2 gas, or this and PH3 gas or B2H6 gas (both at 11000p).
A gas mixed with 403 CCM (p hydrogen gas dilution) was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid Si particles 114, heated in an electric furnace 113, kept at 1100°C to melt the Si, and injected SiF4 into it from a cylinder through the SiF4 introduction pipe 115. , the active species of S r F2 is generated, and the inlet tube 11
6 and then introduced into the film forming space 101.

The atmospheric pressure in the film forming space 101 is set to 0. A non-doped or doped a-5i film (thickness 700A
) was formed. The film formation rate was 35 A/sec.

Then, the obtained non-doped or p-type a-3i
After placing the film sample in a deposition tank and forming a comb-shaped AI gap electrode (length 250p, width 5mm) at a vacuum level of 105 Torr, the dark current was measured at an applied voltage of 10V, and the dark conductivity σ was measured.
The a-Si film was evaluated. The results are shown in Table 1.

Example? H2/F2 instead of H2 gas from the gas supply source 106 etc.
The same a-5i film as in Example 1 was formed except that U gas was used. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, an a-3i film with excellent electrical properties, that is, a high σ value, can be obtained even at low substrate temperatures;
A fully doped a-5i film is obtained.

Example 5 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a membrane structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is a solid Si particle, 205 is an active species raw material introduction tube, 206 is an active species introduction tube, 207 is a motor, and 208 is an active species introduction tube. Heating heater, 209 is a blowing pipe, 210 is a blowing pipe, 211 is an A1 cylinder, 21
2 indicates an exhaust valve. Also, 213 to 216
1 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and is a 217-body gas introduction pipe.

An Al cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. 218, 218... are discharge energy generating devices, and the matching box 21
8a and cathode electrodes 8i and 218b for high frequency introduction.

Further, solid Si particles 204 are packed in one decomposition chamber 202, heated in an electric furnace 203, maintained at 1100°C to melt Si, and SiF is poured therein from a cylinder.

By injecting the active species of 5iF-,
It is introduced into the film forming space 201 through the introduction pipe 206.

On the other hand, H2 is introduced from the introduction pipe 217 into the film forming space 20i. While maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr, plasma is applied to the discharge device 218.

The Al cylinder 211 is heated and held by the heater 208 at 2806C and rotated, and the exhaust gas is passed through the exhaust pulp 2.
Exhaust through 12. In this way, the photosensitive layer 13 is formed.

In addition, the middle layer has been introduced since '6217 H2/B 7I
A mixed gas of 6 (0.2% B2H6 in volume Gi%) was introduced to form a film with a thickness of 2,000.

Comparative Example 1 - Using a general plasma CVD method, SiF4, H2, and B2H are deposited in the film forming space 201 of FIG. 4 at 13.
An amorphous silicon deposited film was formed using a 56 MHz high frequency device.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 1 and Comparative Example 1.

Example 4 Using the apparatus shown in FIG. 3, the PIN station diode shown in FIG. 2 was manufactured.

First, place the 1000A (7) ITO film 22 on a vapor-deposited polyethylene naphthalate film 21 on a support stand, and
After reducing the pressure to 0-6T o r r, active species of SiF2 are introduced from the introduction pipe 116 and the introduction pipe 110 as in Example 1.
From H2150SCCM, phosphine gas (PH31
000ppm hydrogen dilution) was introduced, 20SCCM of halogen gas was introduced from another system, and 0.000ppm hydrogen dilution was introduced. Plasma was applied from the discharge device 117 while maintaining the ITorr to form an n-type a-5i film 24 (film thickness: 700 Å) doped with P.

Next, the n-type a-
The i-type a-5i film 25 (
A film thickness of 5000 A) was formed.

Next, along with H2 gas, Diporan gas (B2H6100
A p-type a-3t film 26 (film thickness: 700 A) doped with B was formed under the same conditions as the n-type film except for the dilution with hydrogen (0 ppm hydrogen dilution) of 40 SCCM. Furthermore, an Al electrode 27 with a film thickness of 1000 cm is formed on this p-type film by vacuum evaporation, and the PI
An N-type diode was obtained.

The IV characteristics of the thus obtained diode element (area 1 c, m2) were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Figure 3.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
At light irradiation intensity AMI (approximately 100 mW/Cm2), conversion efficiency is 8.5% or more, open circuit voltage is 0.92 V, and short circuit current is 1.
0.5 mA/Cm2 was obtained.

Example 5 The same PIN type diode as in Example 6 was manufactured except that H2/F2 mixed gas was used instead of H2 gas from the inlet pipe 110. Evaluate the rectification characteristics and photovoltaic effect,
The results are shown in Table 3.

From Table 3, it is clear that the present invention has good optical and electrical properties even at a lower plate temperature than the conventional one.
-5i deposited film is obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, I+! ,!
The desired electrical, optical, photoconductive and mechanical properties are improved, and high-speed film formation is possible at a low substrate temperature. In addition, it improves the reproducibility of film formation, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, making it easier to improve film productivity and mass production. can do. Furthermore, effects such as being able to form a film even on substrates with poor heat resistance and shortening the process through low-temperature treatment are exhibited.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. The second UIA is a four-piece diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the tree setting method used in the examples, respectively. 10... Image forming member for electrophotography, 11 Conflicts and bleeds
Base, 12... Intermediate layer. 13... Photosensitive layer, 21... Substrate, 22, 27... Thin film electrode. 24 1 @ a n-type a-Si layer, 25 e I
t a i type a-3i layer, 26 --- p type a-
Si layer, 101.201... Film formation space, 111.202
... Decomposition space, 106.107.108,10
9. 213.214, 215, 216 --- Gas supply source, 103.211 Contents... Substrate, 117.218 --- Discharge energy generating device. 1st 1 Figure 2

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species generated by decomposing a compound containing silicon and halogen, and a film forming raw material gas that chemically interacts with the active species. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing each separately and applying discharge energy to them to excite the film-forming raw material gas and cause it to react.