JPS60249313A - 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 specific silicon compound and compound containing I -family or V- family atoms in a deposition chamber, and by feeding heat energy. CONSTITUTION:A gas atmosphere of silicon compound expressed by a general expression SinHmXr [where, (x) stands for halogen and each of (n), (m) and (r) an integer of 1 or more, and m+r=2n+2] and compound containing I -family or V-family atoms 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 atoms and I -family or V-family atoms is formed on the substrate 2. In order to excite and decompose efficiently, and to deposite a better quality a-Si film, it is desired that the number (n) of silicon atoms in the compound is preferably 3-7, and most suitably 3-5.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a deposited film forming method that uses heat as excitation energy to form a photoconductive film, a semiconductor film, or an insulating film on a predetermined support. More specifically, the present invention relates to a method of forming a deposited film of amorphous silicon (hereinafter abbreviated as a-8i) on a desired support by exciting and decomposing a source gas by applying thermal energy.

[Prior art]

Conventional methods for forming a-8i deposited films include glow discharge deposition and thermal energy deposition using SiH4, Si, and H as raw materials.

That is, these deposition methods are methods in which a deposited film of a-8i is formed on a support by decomposing 8iH or 8i, H6 as a raw material gas using electrical energy or thermal energy (excitation energy). The deposited film is used for various purposes as a photoconductive film, a semiconductor film, an insulating film, etc.

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 achieving a uniform discharge distribution state, and furthermore, the film formation The high-power discharge has a large effect on the film inside the film, making it difficult to ensure the uniformity of electrical and optical properties and quality stability of the formed film, causing disturbances on the film surface during deposition, and damage to the inside of the deposited film. defects 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, in the thermal energy deposition method, the temperature is usually 400°C.
Since the above-mentioned high temperature is required, the support material to be used is limited, and in addition, the probability that useful bonded hydrogen atoms in the desired a-8i will be separated increases, making it difficult to obtain the desired properties.

Therefore, one way to solve these problems is to
A-8i low-heat thermal energy deposition method (thermal CVD) using silicon compounds other than SiH4 and Si2H6 as raw materials
is attracting attention.

This low-calorie thermal energy deposition method uses low-temperature heating instead of glow discharge or high-temperature heating in the above-mentioned methods as excitation energy, and allows the production of a-8i deposited films at low energy levels. It is something that makes it possible. In addition, the lower the temperature, the easier it is to uniformly heat the raw material gas, making it possible to form a high-quality film that maintains uniformity with lower energy consumption than the above-mentioned deposition method. It is easy to control 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 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 while maintaining high quality at a low energy level. An object of the present invention is to provide a thermal energy deposition method that can perform the following steps.

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.

As a result of intensive studies, the present invention has been completed by discovering that these objects can be achieved by using a silicon compound containing halogen atoms as a raw material gas for forming an a-8i film that is decomposed by thermal energy. It is something that

[Summary of the invention]

That is, in the deposited film forming method of the present invention, the following general formula: % formula % (wherein, ) and a compound containing an atom belonging to Group 1 or Group V of the periodic table, and these compounds are excited using thermal energy. The method is characterized in that a deposited film containing silicon atoms and atoms belonging to Group 1 or Group V of the periodic table is formed on the support by decomposing the method.

In the method of the present invention, a silicon compound as a raw material for supplying 8i and a compound containing these atoms for introduction of atoms belonging to Group 1 or Group V of the periodic table are used as raw materials. The deposited film is a deposited film containing silicon atoms and atoms belonging to group Ⅰ or group V of the thoracic table, and can be used for various purposes as a functional film such as a photoconductive film or a semiconductor film. It is.

The raw material for supplying a-8i used in the method of the present invention is a silicon compound containing a halogen atom, and is characterized by being easily excited and decomposed by thermal energy, and has the above general formula. shown.

Among such compounds, n in the above formula is 3 to 7.
is preferably an integer of , more preferably 3 to 6,
Optimally, it is desirable to be an integer of 3 to 5. That is, when the number of silicon atoms in the compound is 3 or more, the bond between adjacent silicon atoms, especially the bond between a silicon atom sandwiched between two silicon atoms and another silicon atom bonded to the atom, It becomes unstable due to relatively low thermal energy and is susceptible to radical decomposition. On the other hand, as the number of directly bonded silicon atoms in the compound increases, radical decomposition becomes easier due to lower thermal energy; however, when the number of bonded silicon atoms is 8 or more, the formed a-8i film This is not preferable because the quality of the product will deteriorate.

Therefore, in order to efficiently excite and decompose and deposit a high-quality a-8i film, the number of silicon atoms in the compound is preferably 3 to 7, more preferably 3 to 6, and most preferably 3 to 6. 5 is desirable.

On the other hand, r halogen atoms represented by X in the above formula are 1
It is not limited to only seeds, but may be a mixture of several types.

The total number of halogen atoms in the compound is m tenn = r
Although determined by the above, it is preferable that the total number of halogen atoms in the compound is smaller than the total number of hydrogen atoms.

The halogen atom contained in the silicon compound used in the method of the present invention is preferably a bromine atom. This is because a silicon-bromine or -iodine bond, particularly a silicon-iodine bond, is more unstable than a silicon-hydrogen bond and is easily excited and decomposed even with low energy such as thermal energy.

The silicon compound used in the method of the present invention is easily excited and decomposed by thermal energy, and has the following properties: SrH, 5
Radicals such as iHX, : 5i2H, : 5iH2X are generated, and these are further thermally excited and decomposed to produce high-quality a
-8i film is formed.

Typical silicon compounds used in the method of the present invention include the following compounds.

&　I　H,5iBr2 A2H, SiI.

A 3 H,8+F ′ A 4 HsSrBr A 5 Hs8iI A 6 H3StFI A 7 H,8tC4'I A 8 H2StBrI A 9 (HBr, Si ) 2 A 10 (HI 2 S l ) 2A 11 (H
, F8i )2 A 12 CH2Ce81)2 A 13 (H, Br8i) 2 A 14 (H, ISx )t A 15 H45i, FI 應16 H48i, CJ! I A 17 ) 58i, BrI A 18 k148 t 1 FB rA 19 Ha
8 it CI BrA 20 Hs 8 t t
P A 21 H, 5i2CI A 22 H, 5i2Br 23 H, Si, I A 26 H, 8igBrH A 27 L 81 s I s A 28 H, 8i, Br.

A29 H4al11’4 & 30 H681B BY 2 A 31 H @ S l @ I 2 & 32H? Si, F & 33 H78ts CI A 34 H7SiB Br A35 HySisI A 36 cyc-H, 5i6Br.

& 37 cyc-H6SiaBra A 38 cyc-H,Si,F,Br6& 39 c
yc I-I, S+6C'/6A 40 cy c H
68t 6 F6A 41 Cy CB2 S 16
F10 In the deposited film formed in the method of the present invention, for example, B, AI! , Ca5In, Te, etc., or group V of the periodic table, such as N, P, As, 8bSBi. Compounds that can be excited and decomposed are used, such as PH, P2H, PF, PF5, PGE1, As
H3, AsP3, AsF,, AsCl5, SbH3
, SbF, , B1H8, BF3, Bα5, BBr3, B
,H,,B4H10,BsHo, BaH5o1BaH
, 2, keces, etc.

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 1 or V of the periodic table are introduced into a deposition chamber, and thermal energy is applied to these compounds. These are thermally excited and decomposed, and a deposited film (a-8i film) containing silicon atoms and atoms belonging to Group 1 or Group V of the periodic table is formed on a support placed in the deposition chamber. Ru.

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

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-8i 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. A gas introduction pipe for introducing a-8i raw material gas 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.degree. 11.12 for supplying raw material gas for a-8i formation and gases such as carrier gas used as needed. In order to measure the flow rate of each gas flowing out from the gas supply source 9゜10.11, 12 toward the deposition chamber l,
Corresponding flow meters 15-1, 15-2, 15
-3°15-4 corresponds to branched gas introduction pipe 17-1
, 17-2, 17-3, and 17-4. Valve 14-1 before and after each 70-meter
, 14-2, 14-3, 14-4.

16-1.16-2.16-3.16-4 are provided,
By adjusting these pulps, a predetermined flow rate of gas can be supplied. 13-1゜13-2.13-3.1
3-4 is a pressure meter 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 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 present invention, the number of gas supply sources 9+10+1it12 can be increased or decreased as appropriate.

That is, when using a single raw material gas, one gas supply source is sufficient. However, when two types of raw material gases are mixed and used, or when a single raw material gas (catalyst gas, carrier gas, etc.) is mixed, two or more are required.

Note that some raw materials do not turn into gas at room temperature and remain liquid, so when using liquid raw materials, a vaporizer (not shown) is installed. There are two types of vaporizers: those that utilize heating and boiling, and those that pass a carrier gas through a liquid raw material.

The source gas obtained by vaporization is introduced into the deposition chamber 1 through a flow meter.

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 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-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 8i,
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, polycyclized vinylidene, polystyrene, polyamide, glass, ceramics, paper, etc. are usually used. Ru.

In particular, in the method of the present invention, the humidity of the support is 150
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. It is now possible to use other supports.

The thin film electrode 22 is made of, for example, NtCr XAes Cr
Mo%Au5Ir, Nb5Ta, V, Ti,
Pt, Pds In, O,, SnO3, ITO
It is obtained by providing a thin film such as (In20B + 8nO2) 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 x 10'λ, more preferably 100 to 5 x 10 s.

In order to make a predetermined layer among the layers constituting the semiconductor layer 27 of the a-8i N-type or P-type as desired, an N-type impurity or a P-type impurity is formed during layer formation. The doping layer may be doped while controlling its amount.

As the P-type impurity doped into the semiconductor layer, atoms belonging to Group 1 of the periodic table, especially, for example, B,
Preferred examples include A/, Ga, In, T1, etc., and N-type impurities include atoms belonging to Group V of the periodic table, especially N1P, As, Sb, etc.
, Bi, etc. are mentioned as suitable ones, but especially B, Bi, etc.
Ga, PSSb, etc. are 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 x 10' to 4 atoms.
Doping should be done within the range of ic%,
In the case of impurities in Group V of the periodic table, 5 X 10-3 ~
Doping may be carried out in a range of 2 atomic%.

In order to dope the above-mentioned impurity into a predetermined layer constituting the semiconductor M27, a raw material for impurity introduction may be introduced in a gaseous state into the deposition chamber 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, raw materials (impurity gas) for introducing such impurities include PH, P, and H for introducing N-type impurities.
,,PF3,PF,,PCl3,As H3,AsF3
,AsF,,AsCe,,S bH,,Sb"11%
BAH8, while BF, BC for P-type impurity introduction.
/, ,BBr,,B,H6,B,H,. , BsH, BaH+o, 1BaI (+t, hect, etc.).

Next, the method for forming the semiconductor N27 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 1O-5T.
orr 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, glow discharge deposition method, S In2,
Since there is no need to heat the support to high temperatures as in thermal energy deposition methods using S 12 Ha as raw material, the energy consumption required for this can be saved.

Next, P-type a-Si is deposited on the thin layer electrode 22 on the support 21.
In order to stack the il, the valve 14-1 of the supply source 9 is filled with the raw material gas for supplying Si as listed above.
．． 16-1 and valves 14-2 and 16-2 of the supply source 10 in which the P-type impurity gas is stored are opened, and the Si supply raw material gas and the P-type impurity gas are mixed at a predetermined mixing ratio. The mixed gas is sent into the deposition chamber 1.

At this time, the flow rate is adjusted while measuring with the corresponding flow meters 15-1 and 15-2. The flow rate of raw material gas is 10 to 1
10008CCM, preferably in the range of 20-500SCCM.

The flow rate of the P-type impurity gas is determined from the flow rate of the source gas multiplied by 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 stored and used in a diluted state with H2 gas or the like to a predetermined concentration.

The pressure of the mixed gas in the deposition chamber 1 is 10-2 to 100 Torr.
, r, preferably maintained in the range of 10-'' to I Torr.

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

Decomposition products other than a-St and P-type impurity atoms, undecomposed surplus raw material gas, etc. are exhausted through the gas exhaust pipe 20, while new raw material mixed gas is continuously passed through the gas introduction pipe 17. supplied to P-type a-8i12
3 is formed.

It is desirable that the number of P-type a-8iO Naratsu is in the range of 100 to 104 people, preferably 300 to 2000 people.

Next, the pulp 14-1. connected to the gas supply source 9.10.
16-1.14-2.16-2 are all closed to stop the introduction of gas into the deposition chamber 1.

After the gas in the deposition chamber is exhausted by driving an exhaust device (not shown), the pulp 14-1, 16-1 is opened again, and the raw material gas for supplying Si is introduced into the deposition chamber 1. Suitable flow conditions and pressure conditions in this case are the same as those for forming P-type a-8i@23.

In this way, non-doped, i.e., ■-type a-8il
fif24 is formed.

The 1-thickness of the type (2) a-8i layer is preferably in the range of 500 to 5 x 104 layers, preferably 1000 to 10,000 layers.

Next, a gas supply source 11 in which N-type impurity gas is stored.
Open the pulp 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, 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 25 is 1. OO-10'
The number of people is preferably in the range of 300 to 2,000 people.

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. 5 to 50 people/s because it is easily excited and decomposed by
A layer formation rate as high as ee can be obtained.

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.

According to the method of the present invention, in addition to forming a single semiconductor of the PIN type diode device described above, a- 8i- can be formed. Further, in the examples explained above, the deposited layer was formed under reduced pressure, but the present invention is not limited to this, and the method of the present invention can be carried out under normal pressure or under increased pressure as desired. .

As described above, according to the method of the present invention, thermal energy with a low calorific value is used as excitation energy, and by using a raw material gas that is easily excited and decomposed by the thermal energy, the film formation rate is high and the energy is low. a- at level
It has become possible to form an 8t 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 It became possible to form the film uniformly and with high precision.

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

Example 1 Using the apparatus shown in FIG. 1, the silicon compound plate 1 mentioned above was used as a raw material for supplying Si, and B 2 Ha was used as a gas for introducing P-type impurities to dope B atoms. The formation of P-type a-8i@ was carried out as follows.

First, the support 2 (Corning≠7059, transparent conductive film (polyester paste)) is set on the support stand 3 in the deposition chamber 1, and the entire gas exhaust pipe 20 is passed through the deposition chamber 1 using an exhaust device (not shown). Reduce the pressure to 10' Torr,
The heater 4 is energized to maintain the support temperature at 220°C.
Next, the P-type impurity introducing gas B2H is diluted with the pulp 14-1.16-1 of the raw material supply source 9 filled with silicon compound A1 and H2 (dilution rate 0.025 molt).
Pulp 14-2.16 of raw material source 10 filled with 6
-2 were opened, and the raw material mixed gas was introduced into the deposition chamber 1.

At this time, while measuring with the corresponding flow meters 15-1 and 15-2, the gas consisting of silicon compound store 1 and B2H,
Gas B/Si = 5 x 10-” mol
/mol, and the flow rate of the mixed gas is 1.
Each flow rate was adjusted to 508 CCM. Next, a P-type a-8i layer with a layer thickness of 400 people (B atom content of 5
X 10' atomic%) was deposited on the support 2 at a deposition rate of 47 people/see.

Note that the thermal energy was uniformly applied to the gas flowing near the entire surface of the support 2 disposed in the deposition chamber 1. At this time, decomposition products other than a-8i and B atoms, undecomposed surplus raw material gas, etc. are removed from the gas exhaust pipe 20.
Meanwhile, new raw material mixed gas was continuously supplied through the gas introduction pipe 17.

A-8 thus formed by the method of the present invention
The evaluation of t lit is based on the a-8it- formed on the substrate.
A comb-shaped Al gap electrode (
The dark current was measured by measuring the dark current and calculating the dark conductivity σd.

Note that the gap electrode is a
-8i- is placed in the vapor deposition tank, and the iron tank is heated to 10"6 Torr once.
After reducing the pressure to a vacuum level of r, the vacuum level is reduced to 10' Torr.
The deposition rate was adjusted to 20λ/! AJ was deposited on the A-8i layer to a layer thickness of 1500 using .

The obtained dark conductivity σd is shown in Table 1.

Examples 2 to 7 Each of the silicon compounds A6, A14, A24, A26, and 30.432 (Examples 2 to 7) listed above was used individually as a raw material for supplying Si, and the same procedure as in Example 1 was carried out. to form a P-type a-8i l membrane, and the obtained a-3i
The σd of the layer was measured in the same manner as in Example 1. The measurement results are shown in Table 1.

Comparative Example 1 A P-type a-8i layer was formed in the same manner as in Example 5 except that 5t2H was used as the raw material for supplying a-8i, and the σd of the obtained a-3ilii was the same as in Example 1. It was measured using The measurement results are shown in Table 1.

Example 8 B2H, gas PH for introducing N-type impurities diluted with H2 (dilution rate 0.05 molt) instead of gas supply source 9
Using the raw material supply source 11 filled with No. 3, the flow rate of PH and gas is such that the mixing ratio of the PH and the gas consisting of silicon compound &2 is P/5i-5x10' mol/mol
And the flow rate of these mixed gases is 1508CCM
An a-8i layer (layer thickness: 4,000 layers) doped with P atoms, which are N-type impurities, was formed in the same manner as in Example 1, except that the following was adjusted. A comb-shaped Al gap electrode was also provided on the formed N-type a-8im in the same manner as in Example 1, and the dark conductivity σd was determined. The obtained values are shown in Table 2.

Examples 9 to 14 Silicon compounds A6 and A as raw materials for supplying Si
14, A24, A26, A 30 , 432 (Example 9
~14) were used individually to form an N-type a-8i sound in the same manner as in Example 8, and the σd of the obtained a-8i layer was measured in the same manner as in Example 1. Table 2 shows the measurement results.
Shown below.

Comparative Example 2 An N-type a-8i tank was completely formed in the same manner as in Example 12 except that 5i2H was used as the raw material for Si supply, and σd of the obtained a-8t was determined in the same manner as in Example 1. It was measured. The measurement results are shown in Table 2.

Examples 15-28 When forming a P-type a-8i layer by setting the support temperature at 250°C and using the silicon compounds shown in Tables 3 and 4, the procedure was the same as in Example 1, and N When forming a type a-8i layer, P type and N type a-8
A total of 14 i-layers, 7 each, were formed. The σd of the obtained a-8i1m was measured in the same manner as in Example 1.

ω1'' constant results are shown in Tables 3 and 4.

Comparative Examples 3 and 4 P-type a-8t@ was produced in the same manner as in Example 15 except that 5i2H was used as the raw material for Si formation (Comparative Example 3)
, Further, two types of a-8i@ of N-type a-8i@ (Comparative Example 4) were formed in the same manner as in Example 22, and the obtained a-8il
- σd was measured in the same manner as in Example 1. The measurement results are shown in Tables 3 and 4.

To summarize the results of Examples 1 to 28 and Comparative Examples 1 to 4 above, as shown in the evaluation results in Tables 1 to 4, the film formation rate was lower when the support temperature was 220°C. The film formation rate in Comparative Examples 1 and 2 was 1 OA/see
In contrast, Example 1 of the present invention. The film formation rate in Z, 8.9 was 4'7 people/see, and when the support temperature was 250°C, the film formation rate in Comparative Examples 3 and 4 was 11λ/see. On the other hand, in Examples 15 and 22 of the present invention, a good film formation rate of 49λ/See was obtained, and in any case of Examples 1 to 28 of the present invention, Sufficient doping efficiency was obtained, and a-8t@ having a high dark conductivity σd'ft: was formed.

Example 29 Using the apparatus shown in Fig. 1, using the silicon compound A1 mentioned above as the raw material for supplying St, setting the support temperature to 220°C, and setting the PIN as shown in Fig. 2. Formation of the type diode device was performed as follows.

First, the support 21 with the thin film electrode 22 (100 OA of ITO deposited on glass) was set on the support stand 3 in the deposition chamber 1, the operating conditions were the same as in Example 1, and the raw material supply source 9
and 10, silicon compound A1 and B2H6 gas were introduced into the deposition chamber 1 to form a P-type a-8i layer 23.

Next, when the thickness of the P type a-8ilii 23 reaches 400, the pulp 14 connected to the gas supply source 9.10
-1.16-1.14-2.16-2 are all closed to stop the introduction of gas into the deposition chamber 1. After the gas in the deposition chamber is removed by driving an exhaust device (not shown), the pulp 1 is again pumped.
4-1゜16-1 was opened, and 150 SCCM of raw material gas consisting of Si supplying silicon compound boiling 1 was introduced into the deposition chamber 1.
A-8i, which is non-doped, i.e.
@ 24 (Jfj thickness, 5000 people) P type a-Si1
It was formed at the same rate as in the formation of No. 23.

Next, the pulp 14-3° 16-3 connected to the gas supply source 11 in which the N-type impurity introducing gas PH, diluted with H2 (dilution rate 0.05 mol%) is stored, is opened, and the deposition chamber 1 PH3 gas was introduced into the N-type a-3i layer 25 doped with P atoms using the operating conditions in Example 6.
(layer thickness: 400 layers) was deposited on the I-type a-8i layer 24 at the same rate as in the formation of the P-type a-8i layer 23, and the three a-
A semiconductor layer 27 made of 8i 23.24.25 was created.

Thus formed by the method of the present invention. PIN
A vacuum evaporation method (pressure I
A PIN type diode is formed by stacking M thin film electrodes (26'f) with a film thickness of 1000 using
Completed device.

The rectification characteristics (ratio of forward current and reverse current at a voltage of 1 V), n value (current equation of P-N junction J
= J (n value at exp (eV/nkT)-i 1) and light irradiation characteristics (conversion efficiency at 100 mW/d light irradiation intensity, open circuit voltage, short circuit current) were evaluated. The results are shown in Table 5.

Examples 30 to 41 The silicon compounds A6, A10, Ya11, A14, Ya24, and A26 listed above were used as raw materials for Si supply.
,A27,ya30,A32,A36,bian38,A
41 (Examples 30-41) were individually used to prepare a three-layer PIN type a-8i in the same manner as in Example 29.
A semiconductor layer was formed, a PIN type diode device was produced, and the rectification characteristics, n value, and light irradiation characteristics were evaluated in the same manner as in Example 29. The results are shown in Tables 5 and 6 - Comparative Example 3 A three-layer PIN type a-8i semiconductor # was entirely formed in the same manner as in Example 29 except that 5i2H was used as the raw material for Si supply, and the PIN A type diode device was created. Example 2 Regarding the rectification characteristics, n value, and light irradiation characteristics of the created PIN type diode device
It was evaluated in the same manner as 9. The results are shown in Table 5.

Examples 42-54 Support temperature set at 250"C and Tables 7 and 8
A 3m-structure PIN type a-8i semiconductor layer was formed in the same manner as in Example 29, except that the silicon compound shown in Example 29 was used, and 12 PIN type diode devices were created, and rectification was performed in the same manner as in Example 29. The characteristics, n value, and light irradiation characteristics were evaluated. The results are shown in Tables 7 and 8.

Comparative Example 4 A PIN type a-8i semiconductor 1@ with a 3@ structure was formed in the same manner as in Example 42 except that 5i2L was used as the raw material for supplying Si, and a PIN diode device was produced. Example 2 for each of the rectification characteristics, n value, and light irradiation characteristics of the created PIN type diode device
Evaluation was made in the same manner as in 9. The results are shown in Table 7.

Summarizing the results of Examples 29 to 53 and Comparative Examples 3 and 4 above, the PINs formed in Examples 29 to 53
The rectification ratio of the W diode device is expressed as a common logarithm of 7.0 to 8.6, which shows good rectification characteristics, and the conversion efficiency is 7.2 or more, the open circuit voltage is 0.7 V, and the short circuit current is 12 Good light irradiation characteristics of .5 mA/cA were obtained.

[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. 1.Deposition chamber 2, 21: Support 3.Support stand 4: Heater 5: Conductor 6-1.6-2.6-3: Gas flow 9.10, 11, 12: Gas supply 3 combined source 13- 1.13-2.13-3.13-4゜18: Pressure meter 14-1.14-2゜14-3.14-4.
16-1.16-2゜16-3.16-4.29 + valve 15-1.15-2.15-3.15-4 + flow meter 17.17-1.17-2.17-3.17 -4
: Gas inlet pipe upper P-sha 20: Gas exhaust pipe 22, 26: Thin film electrode 23: P type a-3i layer 24: ■type a-5i layer 25
: Nga-s i! 27. Semiconductor layer 28: Conductive wire applicant Canon Corporation

Claims (1)

[Claims] (1) In the deposition chamber in which the support is placed, the following general formula; A gaseous atmosphere is formed between the silicon compound shown and a compound containing atoms belonging to Group I or Group V of the periodic table, thermal energy is applied to these compounds, and silicon atoms and periodic compounds are formed on the support. 1. A method for forming a deposited film, comprising forming a deposited film containing atoms belonging to Group 1 or Group V of the Table of Contents.