JPS60251615A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To form a deposited film containing silicon atom at low energy level by a method wherein specific chain halogenated silicates, other compounds comprising elements belonging to the groups III or V in the table of periodic law and gaseous atmosphere of hydrogen are formed in a chamber containing a substrate. CONSTITUTION:Chain halogenated silicates represented by a molecular formula I [wherein X and Y, (n), (m) and (l) respectively represent different kind of halogen atoms, integer of 1-6, integer exceeding 1 and (m+l)=2n], other compounds comprising elements belonging to the groups III or V in the table of periodic law and gaseous atmosphere of hydrogen are formed in a chamber containing a substrate while the compounds are excited and decomposed by utilizing thermal energy to form a deposited film containing silicon doped with impurity element on the substrate. The chain halogenated silicate is a halogen derivative of straight chain or branched chain hydrogenated silicon (chain silane compound) SinH2n+2 to be used together with two or more kinds of them.

Description

[Detailed Description of the Invention] [Field of Application in M Industry] The present invention utilizes heat as excitation energy to form a photoconductive film, a semiconductor, or an insulating film on a predetermined support. More specifically, regarding the method, in particular, amorphous silico/(hereinafter a-
8i).

[Prior art]

Conventionally, methods for forming a-8i deposited films include 8iH,...
A glow discharge deposition method and a thermal energy deposition method using Si2H as a raw material are known. That is, these deposition methods 4 use SiH as the raw material gas, Si
This is a method in which 2H6 is decomposed using electrical energy or thermal energy (excitation energy) to form a deposited film of a-8i on a support, and the deposited film formed can be a photoconductive film, a semiconductor film, an insulating film, etc. It is used for various purposes.

However, in the glow discharge deposition method in which the deposited film is formed under high-power discharge, it is difficult to control stable conditions such as nrt, where a uniform discharge distribution cannot always be obtained. Furthermore, the effects of high-power discharge on the film during film formation are significant, making it difficult to ensure the uniformity of electrical and optical properties and quality stability of the formed film, and causing disturbances on the film surface during deposition. , defects in the deposited film are likely to occur. In particular, it has been extremely difficult to form a thick deposited film with uniform electrical and optical properties using this method.

On the other hand, the thermal energy deposition method also requires a high temperature of 400°C or higher, which limits the support materials that can be used, and in addition, useful bonded hydrogen atoms in the desired a-8i are separated. Since the vitreous ratio increases, it is difficult to obtain the desired properties.

Therefore, one way to resolve these nodal points is to
A -8i low heat ■ thermal energy deposition method (thermal CVD) using silicon compounds other than 8iH4 and 8i2H as raw materials
) is attracting attention.

This low-calorie thermal energy deposition method uses low-temperature heating instead of gelatin discharge or high-temperature heating in the above-mentioned methods as excitation energy, and allows the production of a-8i' deposited films at a low energy level. 〇In addition, the lower the temperature, the easier it is to uniformly heat the raw material gas, resulting in high-quality film formation that maintains complete uniformity with lower energy consumption than the deposition method described above. In addition, manufacturing conditions can be easily controlled and stable reproducibility can be obtained, and there is also the advantage that there is no need to heat the support to a high temperature and that selectivity to the support can be expanded.

[Purpose of the invention]

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

Another object of the present invention is to form a high-quality deposited film that ensures uniformity of electrical and optical characteristics and stability of 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]

The above purpose is to install the general formula SinXm in the room that houses the entire base.
Yl (X and tjY are each different halogen atoms, n is an integer of 1 to 6, m and ) are each an integer other than l, and m+1-=2n+2. ), a compound containing an element belonging to Group Ⅰ or Group Ⅰ of the periodic table (hereinafter referred to as an impurity element) and hydrogen, and generates a gaseous atmosphere, and generates thermal energy. This is achieved by a method for forming a deposited film, which is characterized in that the compound and hydrogen are excited and decomposed by utilizing the silicon t-containing deposited film doped with an impurity element on the substrate.

In the method of the present invention, a silicon compound is used as a raw material and a raw material for supplying SI, and a compound containing these atoms is used for introducing atoms belonging to group ① of the periodic table. The deposited film is a deposited film containing silicon atoms and atoms belonging to Group Ⅰ or Group Ⅲ of the periodic table, and can be used for various purposes as a functional film such as a light guide film or a semiconductor film. It can be used for

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 halogen derivative of 8 inH, n+, and is a compound that is easy to manufacture and has high stability. In the general formula, X and Y represent different halogen atoms selected from fluorine, chlorine, bromine and iodine, respectively. The value of n is 1
The reason why n is limited to 6 is because as n becomes larger, decomposition becomes easier, but it is also difficult to synthesize a substance that is difficult to vaporize, and the decomposition efficiency becomes worse.

Preferable a M of the chain halogenated silicon compound of the above general formula are listed below.

■ Compound containing F and Cl gold: SiFH]C4-m (m tf 1 to 3) an integer), 8itFmC/am (m is an integer from 1 to 5), 8
i3FmcA'g-m, (m is an integer from 1 to 7),
814 FmCA! to-m (m is an integer from 1 to 9)
, ■ Compounds containing F and Br: S1FrnBr4-In (rn fi an integer of 1 to 3), 8 i2FmBr, -m (m is an integer of 1 to 5), Si3FmBr, -111 (m is an integer of 1 to 5) 7), Si, FmHr 1O-In (m is an integer of 1 to 9), ■ Compound containing C1 and Br S 1C4B Br4-m (m is an integer of 1 to 3),
S i2c7mBr, -m (m 1l - an integer from 1 to 5), 81s (4mBr8 - m (m is an integer from 1 to 7)
, S i4 Clm B rlO=m (" is an integer of 1 to 9), ■ Compound containing F and 1: S i FmI, -m (m trJi an integer of 1 to 3)
1, Si, PHII6-m (m is an integer from 1 to 5).

Among the above ■ to ■, the most preferable ingredient f4 is as follows:
The following compounds may be mentioned. .

(1) SiF, C7, (2) SiF, C4, (3
) SiF, C7.

(4) Si, FC! ,,(5) 5i2F2(J4,
(6) 5j2k”3C4r(7) S 12F4C
4, (8) S j2Picl, (9) S 1aF7
'cノ.

(10) Sis”o”llt r (11> 5ts
F, C4j (12) SiF, Br.

(13) Si, li”2Br2 + (14) S
iF'Br,, l (15) Si,F,Br.

(16) 8i, F, Br2. (17) Si, F3
Br3, (18) 5iCA! , Br.

(19) 5tC4Br2 + (20) 8xC7l
Brss (21) 5tFBI *(2shi8iF21
2゜In the present invention, by forming a gaseous atmosphere of a chain silicon halide compound of the general formula above, a compound containing an impurity element, and hydrogen in the chamber, hydrogen generated in the process of excitation-decomposition reaction can be removed. Radicals increase the efficiency of the reaction. Moreover, hydrogen is incorporated into the deposited film that is formed.
Purple plays a role in reducing defects in the S1 bond structure. In addition, the chain halogenated silicon compound of the general formula is decomposed into SiX, SiX, , 5iX8. Si, X,
.

5i2X4, SigX, , Si, X, , 8
iY, 8iY2', 5iY1.

S 12Y3 , Si, Y, , Si! Y, ,
Si, Y, , 5iXY, 5iXY2゜S 1
2XY2 , S 12XY3 , 5i3X Y, ,
8iBX, Y2, si,,xY4゜ generates radicals of Si, After going through four anti-rubbing processes including
, X or Y, a high-quality film with a low localized level density can be obtained.

The linear halogenated silicon compound having the above general formula is 2
Although more than one type of these compounds may be used in combination, in this case, it is possible to obtain properties that are equivalent to the average of the film properties expected by each compound, or properties that are synergistically improved.

For example, B,
Group II of the periodic table such as AI, Ga, In, TI, etc. or N
, P, A, s, Sb, Bi, etc., are used as raw materials for introducing atoms belonging to group Ⅰ, such as compounds containing these atoms and easily excited and decomposed by thermal energy. Such compounds include nl such as P
H8, P2H,, PF3. PF, , PCI, ,
AsH3,'AsF3. Ash, , AsCl,
, 8b) i3. S, bF', , BiH3゜B
P, , BCl2, BBr, , B2H2,B
, H5゜, B, H(,.

B, H, o, B6H,2, AlCl3, etc. can be mentioned.

In the method of the present invention, a silicon compound as described above in a gaseous state and a compound containing an atom belonging to Group M or Group II of the periodic table are introduced into a deposition chamber, and thermal energy is applied to these compounds. These are excited and decomposed, and a deposited film (containing silico/atoms and atoms belonging to group M or
a-8i film) is formed.

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. An embodiment using a Joule heat generating element will be explained.The heater is brought into contact with or close to the back surface of the support to conductively heat the support surface, thermally excite and decompose the raw material gas near the surface, and the decomposition products are transferred to the support surface. to be deposited.

Alternatively, it is also possible to place the heater close to the surface of the support.

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

No. 11iJ has a light 4m film made of a-8i on the support,
1 is a schematic configuration diagram of a deposited film forming apparatus for forming a functional film such as a semiconductor film or an insulating film.

Formation of the deposited film takes place inside the deposition chamber 1.

This is a support stand on which three supports are placed inside the deposition chamber 1.

4 is a heater for heating the support, and conductive, tj! 5 supplies power to the heater 4. a-8i in deposition chamber 1
The inside of a gas introduction pipe for introducing raw material gases and gases such as a carrier gas to be used as necessary is connected to the deposition chamber 1. The other end of this gas introduction pipe 17 is a-8i
Gas supply sources 9, 10゜11 for supplying forming raw material gas and gases such as carrier gas used as necessary
．． It is connected to 12. Gas supply source 9゜10.11.
In order to measure the total flow rate of each gas flowing out from 12 toward the deposition chamber lVc, a corresponding flow meter 15-1,
15-2, 15-3゜15-4 or a branched gas introduction pipe 17-1゜17-2, 17-3, 17-4
17) Before and after each 70-meter provided on the way [
Valve 1.4-1゜14-2, 14-3, 14
-4, 16-1, 16-2.

16-3.16-4 are provided and these valves are connected to Hl
tb to supply a certain amount of gas.

13-1, 13-2, 13-3, and 13-4 are pressure meters for measuring the pressure on the high pressure side of the corresponding flow meter.

The gases that have passed through the flow meters are mixed and introduced into the deposition chamber l under reduced pressure by an exhaust system W (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.

For gas exhaust, the other end of the kidney is connected to an exhaust device (not shown).

In the present invention, the gas gi supply @i9 and the quantity WI of 10.11°12 can be increased or decreased as needed.

In other words, when using a single raw material gas, only one gas supply source is sufficient. However, when using a mixture of two types of raw material gases, or when mixing (catalyst gas, carrier gas, etc.) with the firefly raw material gas, two or more gases are required.

Note that some of the raw materials do not turn into gas even after 7 years and remain as adults, so when using liquid raw materials, a vaporizer (not shown) is installed. There are those that utilize a flower, #, those that allow a carrier gas to pass through the raw material of the main body, etc. The raw material gas obtained by vaporization is introduced into the deposition chamber 1 through a floater.

A typical PI using the apparatus shown in FIG.
Using an example of how to form an N-type diode device,
The method for forming an a-8i deposited film of the present invention will be explained in more detail.

FIG. 2 is a schematic cross-sectional view illustrating 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-8i layer, 24 is a ■ type a-8i layer, and 25 is an N type a
-8i layer, 27 is a semiconductor layer, and 28 is a conductive wire. The support 21 is semiconductive, preferably electrically insulating. Examples of the semiconductive support include St,
Examples include a plate made of a semiconductor such as Ge.

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, ceramics, paper, etc. are usually used. be done.

In particular, in the method of the present invention, the temperature of the support is 150°C.
Among the materials for forming the above-mentioned support, materials with low heat resistance that cannot be applied to conventional glow discharge deposition methods or thermal energy deposition methods can be used. It has now become possible to use supports made of

The thin film electrode 22 is made of, for example, NiCr + Al t Cr.
, Mo.

Au, Ir, Nb, Ta+V, Ti, P
t, Pd, In, 03+ 5nOt +ITO(I
It can be obtained by forming a thin film such as ntOs +5nOz) on a support using a method such as vacuum evaporation, electron beam evaporation, or sputtering.

The film thickness of the electrode 22 is desirably 30 to 5 x 10'A, more preferably 100 to 5 x 10'. In order to make the layer N-type or P-type as desired, an N-type impurity or a P-type impurity may be doped into the formed layer while controlling its amount during layer formation.

P-type impurities doped into the semiconductor layer include atoms belonging to Group Ⅰ of the periodic table, especially B,
Preferred examples include AI, Ga, Ins T1, etc., and preferred N-type impurities include atoms belonging to Group Ⅰ of the periodic table, particularly N1P, As%sb%Bi, etc. , especially 8%Ga, P%sb
etc. is optimal.

In the present invention, in order to impart a desired conductivity type, the semiconductor layer 2 is
The amount of impurities to be doped into 7 is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities from group Ⅰ of the periodic table, it is 3×10 to 4 atoms.
It is sufficient to dope the doping so that the impurity falls within the range of
It is sufficient to dope the material so that it falls within the range of es.

In order to dope a predetermined layer among the layers constituting the semiconductor layer 27 with the above-mentioned impurity, it is sufficient to introduce a raw material for impurity introduction into the deposition chamber in a gaseous state during layer formation. As the raw material for introducing such impurities, those which are in a gaseous state at room temperature and pressure, or which can be easily gasified under at least layer-forming conditions or by a vaporization device, are employed.

Specifically, the raw material (impurity gas) for introducing such impurities is PH3+ Pt for introducing N-type impurities.
H4+ PF3 + PFa + PCl5 + As
Hs +AsF5 l AsF5 + AsC15+
5bHs + 5bFs HBiH3%; for introducing monodispersed impurities, BF, BCl3. BBr, .

B2H6, B4H1O, B-Ha, BeH+o, B
6HI2, AlCl5, etc. can be mentioned.

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

First, the support 21 on which the thin layer of the electrode 22 is attached is placed on the support stand 3 in the deposition chamber 1, and the air in the deposition chamber is evacuated through the gas exhaust pipe 20 by an exhaust device (not shown) to reduce the pressure. . The atmospheric pressure inside the deposition chamber under reduced pressure is 5 x 10'To
rr or less, preferably 10 Torr 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 200 to 250°C.

As described above, since the support temperature is relatively low in the method of the present invention, it is possible to use the glow discharge deposition method or 5IH4r5.
Since there is no need to heat the support to high temperatures as in thermal energy deposition methods using t2n8 as raw material, the energy consumption required for this purpose can be saved.

Next, in order to stack a P-type a-8i layer on the thin layer electrode 22 on the support 21, a supply source 9(7)/( loop 14-
1.Open the valves 14-2 and 16-2 of the supply source 1o in which the P-type impurity gas is stored, and
A mixed gas containing a supply source gas and a P-type impurity gas mixed at a predetermined mixing ratio is fed into the deposition chamber l.

At this time, the flow rate is adjusted while being measured by the corresponding flow meter 15-1, 15-2. The flow rate of raw material gas is 10 to 1
A range of 100OSCC, preferably 20 to 50°SCCM is desirable.

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

However, since the amount of impurity gas mixed is extremely small, in order to facilitate flow rate control, impurity gas is usually stored and used in a diluted state with H, gas, etc. to a predetermined concentration.

The pressure of the mixed gas in the deposition chamber 1 is 10 to 1 oTorr,
It is desirable to maintain it preferably in the range of 10 to 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-8t and trace amounts of P-type impurity atoms are transferred onto the support. is deposited in

a Non-Si and P-type impurity atoms, other decomposition products, undecomposed surplus raw material gas, etc. are discharged through the gas exhaust pipe 20, while new raw material mixed gas is continuously supplied through the gas introduction pipe 17. supplied, P-type a 84 layer 2
3 is formed.

The layer thickness of P type a-8i is 100 to 104 people, preferably i
L< is preferably in the range of 300 to 2,000 people,
Valve 14-1.16- connected to gas supply source 9.10
1.14-2.16-2 All are closed and the introduction of gas into the deposition chamber 1 is stopped. By driving an exhaust device (not shown),
After removing the gas in the deposition chamber, close the valve 14-1.1 again.
6-1 is opened, and the raw material gas for supplying Si is introduced into the deposition chamber 1. In this case, the preferred flow rate and pressure conditions are P-type a
The conditions are the same as those for forming the -8t layer 23.

In this way, the non-doped, ie, ■-type a-8i layer 2
4 is formed.

The thickness of the type (2) a-8i layer is 500-5×10'A, preferably in the range of 1000 to 10,000.

Next, a gas supply source 11 in which N-type impurity gas is stored.
Open the valve 11-3.16-3 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, as in the case of determining the flow rate of the P-type impurity gas.

In the same way as when forming the P-type a-8i 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-8i is transferred to the support. The N-type a-8i layer 25 is formed by being deposited thereon and a trace amount of N-type impurity atoms from decomposition products mixed into the deposit.

The thickness of the N-type A-8I layer 250 is desirably in the range of 100 to 104, preferably 300 to 2,000.

In the formation of the P-type and N-type a-8i 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. Because it is easily excited and decomposed by
It is possible to obtain a layer formation rate as high as c.

Finally, a thin layer electrode 26 is formed on the N type a-8i layer 25 using the same method as the thin layer electrode 22 to have the same layer thickness as the thin layer electrode 22, and a PIN type diode device is completed. Ru.

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

Incidentally, according to the method of the present invention, in addition to forming the conductor layer of the PIN type diode device described above, it is possible to form a single layer or multilayer a-81 layer having desired electrical and optical characteristics. can be formed. In the example described above, the deposited layer was formed under reduced pressure, but the method of the present invention is not limited to this, and the method of the present invention may be performed under normal pressure or under increased pressure, as desired. can.

According to the method of the present invention as described above, the excitation energy -
By using a low amount of thermal energy and using a raw material gas that is easily excited and decomposed by the thermal energy, a high film formation rate can be achieved at a low energy level.
It has become possible to form a -8i deposited layer, and it has become possible to form an a-8i deposited layer with excellent uniformity of electrical and optical properties and stability of quality. Therefore, in the method of the present invention, supports made of materials with low heat resistance that cannot be applied to conventional glow discharge deposition methods or thermal energy deposition methods can be used, and the high temperature of the supports can also be used. It has become possible to save energy consumption required for heating.

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

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

Example 1 The above-mentioned exemplified compounds (1), (2), (?), or (8) were used as the chain silicon halide compound of the general formula, and B2H6 was used as PH3 as the compound containing an impurity element. , P as an impurity was detected using the apparatus shown in FIG.
An a-3i 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.
The inside was evacuated and the pressure was reduced to 1 (lIliTorr).The support temperature was set at 250°C, and the silicon halide compound in a gaseous state and PH3 gas or B2H6 gas were mixed in a ratio of 1:5X10-3. 1l10 of the residue mixed with
3CC and hydrogen gas were introduced into the deposition chamber at a flow rate of 403CCM, and the atmospheric pressure in the chamber was reduced to 0. A doped a-3t film was formed by maintaining the temperature at ITorr. Film deposition speed is 30 people/
It was sec.

For comparison, an a-3i film similarly doped with [7] was formed using S i 2H6. The film formation rate was 10 persons/sec.

Next, the obtained a-3T film sample was placed in a vapor deposition tank, and after forming a comb-shaped All gear and electrode (length 250 mm, width 5 mm) at a vacuum degree of 1 O-5 Torr, an applied voltage of 10 V was applied. Measure the dark current and calculate the dark conductivity σd, a-3
The t membrane was evaluated.

The results are shown in Table 1.

From Table 1, compared to the case of using conventional 5i2)(6), a-3zg according to the present invention can obtain sufficient doping efficiency and high σd even at a low substrate temperature.

Example 2 The substrate was a polyimide substrate, the support temperature was set at 250°C, and the exemplified compounds (12), (13), and (15) were used as the chain halogenated silicon compounds of the general formula. An a-3i film was formed in the same manner as in Example 1, and σd was determined.

The results are shown in Table 2.

Table 2 Example 3 The exemplified compounds (1), (2), (7), and (8) were used as the linear silicon halide compounds of the general formula, and the apparatus shown in FIG. The PIN type diode shown was manufactured.

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-3i film 24 (film thickness: 400 layers) was formed in the same manner as in Example 1. 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.
A type 1 a-3i film 25 (thickness: 5,000 Torr) was formed in the same manner as the P5a-3i film except that the pressure was 5 Torr.

Then, N doped with P in the same way as in Example 1
A type film-5i film 26 (film thickness: 400 mm) was formed. Note that the heat application conditions were the same as those for the P type. Furthermore, on this N-type film, a film thickness of 100 mm (7) AsL electrode 2 was formed by vacuum evaporation.
7 was formed to obtain a PIN type diode.

For comparison, a PIN diode was similarly formed using Si2H6.

I of the diode element thus obtained (area 1 cm2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Table 3.

From Table 3, it can be seen that the deposited film according to the invention provides superior rectification properties even at low substrate temperatures compared to the case using conventional Si 2H6.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
Light irradiation intensity AMI C approximately 100mW/cm2), conversion efficiency 7%, open end voltage 9.7V, short circuit type f&l OmA
/ Cm2 was obtained.

Example 4 Transparent conductive film (polyester base) as a substrate
, the above-mentioned exemplified compounds (12) and (+3) as the linear halogenated silicon compounds of the above-mentioned general formula.

(15), a PIN type diode was produced in the same manner as in Example 3 except that the support temperature was set at 250° C., and the rectification ratio and η value were determined. The results are shown in Table 4.

〔Effect 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, even when the film to be formed has a wide area and is thick, uniform electrical and optical characteristics can be obtained and quality stability can be ensured, which is an unprecedented and exceptional 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. , inexpensive and stable to handle.
This has the effect of reducing the risk of fireflies.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram of an example of a deposited film forming apparatus used in the method of the present invention, and FIG. 2 is a schematic cross-sectional view of a PIN type diode device that can be formed by the method of the present invention. l: Deposition chamber 2, 21: Support 3: Support table 4: Heater 5: Conductor 6-1.6-2.6-3 + gas flow 9, 10.11.12: Gas supply source 13-1.13 -2.3-3.13-4.18: Pressure meter 14-1.14-2.14-3.14-4゜16
-1.16-2.16-3.16-4,29: Valve 1
5-1.15-2.15-3.15-4: Flow meter 22.26: Thin film electrode 23: Pfia-3i layer 24:
I type a-3t layer 25: N type a-3i layer 27: Semiconductor layer 28: Conductive wire applicant Canon Co., Ltd.

Claims (1)

[Claims] In the chamber containing the substrate, the general formula: SinXmYl (wherein X and Y are different halogen atoms, n is 1 to 6
, m and l are each an integer of 1 or more, and m
+13=2n+2. ), a compound containing an element belonging to Group M or Group I of the Periodic Table, and hydrogen, and thermal energy is applied to these compounds to form a gaseous atmosphere on the substrate. A method for forming a deposited film, comprising: forming a deposited film containing silicon doped with the above element.