JPS60219735A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To contrive the uniformity of characteristics and the stabilization of quality by forming the gaseous atmosphere of an Si compound expressed by a specific formula with a compound containing atoms belonging to the III group or the V group. CONSTITUTION:Valves 14-1 and 16-1 of a supply source 9 filled with the gas of an Si compound expressed by the formula [R<1> and R<2> represent H or an alkyl radical with the number of carbons 1-3, respectively; (m) represents integers of 3-7, and (n) integers of 1-11] and valves 14-2 and 16-2 of a supply source 10 in which the gas of a P type impurity is stored are opened, and the mixed gas produced by mixing those gases at a fixed mixing rate is fed into a deposition chamber 1. Then, the mixed gas is irradiated with photo energy by driving a photo energy generator 7.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deposited film forming method that uses light as excitation energy to form a photoconductive film, a semiconductor, or an insulating film on a predetermined support. This invention relates to a method of forming a deposited film of amorphous silicon (hereinafter abbreviated as a-9i) on a predetermined support by exciting and decomposing a source gas by applying excitation energy such as light and, if desired, heat. .

Conventionally, methods for forming a-9i deposited films include SiH,
, or 5i2H (,) are known as a glow discharge deposition method and a thermal energy deposition method using SiH4 or Si2H(, as a raw material gas.
2H6 can be converted into electrical energy or thermal energy (excitation energy￥
-) to form a deposited film of a-3i on a support, and the deposited film formed is used for various purposes as a photoconductive film, semiconductor or 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. It has been extremely difficult to form a deposited film that is particularly large in area or thick and has uniform electrical and optical characteristics, and is prone to defects.

On the other hand, thermal energy deposition also requires a high temperature of 400°C or higher, which limits the deposition support materials that can be used. Since the probability of failure increases, it is difficult to obtain desired characteristics.

Therefore, one way to solve these problems is to
A-9i optical energy deposition (photo-CVO) using SiH4 and Si2H6 as raw materials has recently attracted attention.

This optical energy deposition method uses light as the excitation energy instead of glow discharge or heat in the above-mentioned methods, and allows the production of a-Si deposited films at low energy levels. In addition, it is easy to uniformly irradiate the raw material gas with light energy, and it is 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 no need to heat the support to a high temperature, and the selectivity for the support is widened.

However, with such optical energy deposition methods using SiH4 and Si2H6 as raw materials, there is a limit to how much efficient decomposition can be expected, and therefore the film formation speed cannot be improved, making it difficult to mass-produce. It has been pointed out that there is a problem.

The present invention was developed in view of these problems, and it is possible to form a deposited film containing silicon atoms at a low energy level at a high film formation rate while maintaining high quality by using light as excitation energy. An object of the present invention is to provide a light energy deposition method.

Another object of the present invention is to provide uniform electrical and optical characteristics even in the formation of a large-area, thick deposited film.

An object of the present invention is to provide a method capable of forming a high-quality deposited film that ensures quality stability.

As a result of extensive studies, the present invention has achieved these objectives by using at least one azo group directly bonded to a silicon atom as a raw material gas for forming an a-3i film that is decomposed by light energy.
This was accomplished by discovering that this could be achieved by using a silicon compound that has the following properties.

That is, in the deposited film forming method of the present invention, in a deposition chamber in which a support is disposed, the following general formula; is an integer of 3 to 7, and n is an integer of 1 to 11), and a compound containing an atom belonging to Group Ⅰ or Group V of the periodic table is formed. A deposited film containing silicon atoms and atoms belonging to Group I or Group V of the periodic table is formed on the support by exciting and decomposing the compound using light energy. do.

In the method of the present invention, a silicon compound as a raw material for supplying Si and a compound containing these atoms for introduction of atoms belonging to group Ⅰ 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 periodic table, and can be used for various purposes as a functional film such as a photoconductive film or a semiconductor film.

The raw material for supplying Si used in the method of the present invention is a silicon compound having a cyclic structure composed of silicon atoms and carbon atoms, and can be easily excited and decomposed by light energy. It has certain characteristics and is represented by the general formula above.

Among such compounds, m in the above formula is 3 to 7.
is preferably an integer of , more preferably 3 to 6,
Optimally, an integer between 3 and 5 is desirable.In other words, if the number of silicon atoms in the compound is 3 or more, the bond between adjacent silicon atoms, especially the silicon atom sandwiched between two silicon atoms, will be reduced. Bonds with other silicon atoms bonded to this atom become unstable due to relatively low excitation energy and are susceptible to radical decomposition; on the other hand, as the number of directly bonded silicon atoms in the compound increases, even lower excitation energy causes It becomes easier to decompose radicals, but
If the number of tangentially bonded silicon atoms is 8 or more, the quality of the formed a-9i film will deteriorate, which is not preferable.

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

In addition, when the number of carbon atoms constituting the cyclic structure consisting of silicon atoms and carbon atoms in the above formula is 1 to 11, it is easy to synthesize, it is easily gasified, and the decomposition efficiency with light energy is high. Therefore, it is suitable for use in the method of the present invention.

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

H2)12 (CH3)2 1 (CH3)2 (CH3)2 (CH3)2 (CH3)2 (CH3)2 (C)+3)2 (CH3h (CI(3)2 C:H7-Si (CH3) 2 (CH3)2 (CH3)2 (CH3)2 )1 to H3 In the method of the present invention, a silicon compound as described above in a gas state and a silicon compound belonging to Group I or Group V of the periodic table are used. Atom-containing compounds are introduced into the deposition chamber, and these compounds are irradiated with light energy to excite and decompose them, forming silicon atoms and periodic table group II or V A deposited film containing atoms belonging to the genus (
a-5i film) is formed.

In the present invention, light energy refers to energy rays that can provide sufficient excitation energy when irradiated to the above-mentioned raw material gas, and can excite and decompose the raw material gas, and deposit decomposition products. Any wavelength can be used as long as it has a wavelength range. Examples of such light energy include ultraviolet rays, infrared rays, visible light, X-rays, γ-rays, etc., and can be appropriately selected depending on compatibility with the raw material gas.

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

FIG. 1 shows a photoconductive film made of a-3i on a 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 l.

Reference numeral 3 placed inside the deposition chamber 1 is a support base on which the support body 2 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 7 is connected to the deposition chamber 1 for introducing raw material gas for forming an a-Si film and carrier gas used as necessary into the deposition chamber 1.
is connected to. The other end of this gas introduction pipe 17 is connected to a gas supply source 9, 10.11.1 for supplying the raw material gas and gases such as carrier gas used as necessary.
It is connected to 2. Gas supply source 9.10.11.12
In order to measure the flow rate of each gas flowing out toward the deposition chamber l, a corresponding flow meter 15-1.15-2 is installed.
．． 15-3° 15-4 corresponds to branched gas introduction pipe 1
It is provided in the middle of 7-1.17-2°17-3.17-4. Before and after each flow meter there are valves 14-1.
14-2.14-3゜14-4.18-1. +8-2
．． 18-3.1 [1-4 are provided, and by adjusting these valves, a predetermined flow rate of gas can be supplied.

13-1.13-2.13-3.13-4 is a pressure meter, and is 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).

7 is a light energy generator.

If the deposition chamber 1 is not made of a transparent material such as quartz glass, it is sufficient to provide at least a window for irradiating the support 2 with the light energy 8.

In the present invention, the gas supply source 9, +0.11.1
The number of 2 can be increased or decreased as appropriate.

That is, when using a single raw material gas, one gas supply source is sufficient. However, when using a mixture of two or more raw material gases, or when mixing catalyst gas, gear gas, etc. with a single raw material waste, two or more gases are required.

Note that some raw materials do not turn into gases at room temperature and remain liquid, so when using liquid raw materials, heating and boiling must be applied to the 9% conversion equipment in which a vaporizer (not shown) is installed. There are some types that utilize this method, and others that allow a carrier gas to pass through the liquid raw material. The raw material 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 a-9i deposited film forming method of the present invention will be explained in more detail.

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

21 is a support, 22 and 26 are thin film electrodes, 23 is a P-type a-Si layer, 24 is an I-type a-5i layer, and 25 is an N-type a-Si layer.
-9i 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 Si,
Examples include a plate made of a semiconductor such as Ge.

As the electrically insulating support, polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene 1n,
Films or sheets of synthetic resins such as polystyrene and polyamide, glass, ceramics, paper, etc. are commonly used.

In particular, in the method of the present invention, the temperature of the support is set at 50 to
Since the temperature can be relatively low at around 150°C, it is possible to use materials with low heat resistance that cannot be applied to the conventional glow discharge deposition method or thermal energy deposition method among the materials that form the support. It is now possible to use other supports.

The thin film electrode 22 is made of, for example, N1Gr, AI, Cr,
No, Au.

Ir, Nb, Ta, V, Ti, Pt, Pd, In2O
It can be obtained by depositing a thin film of In2O3+ 5n02 or the like on a support using a method such as vacuum evaporation, electron beam evaporation, or sputtering.

The thickness of the electrode 22 is desirably 30 to 5XlO'A, more preferably 100 to 5X103A.

In order to make a predetermined layer among the layers constituting the a-Si semiconductor layer 27 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.

P-type impurities doped into the semiconductor layer include atoms belonging to Group Ⅰ of the periodic table, especially B,
A1. Preferred examples include Ga, In, TI, etc., and preferred N-type impurities include atoms belonging to Group V of the periodic table, such as N, P, As, Sb, Bi, etc. However, especially B, Ga, P,
Sb 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 determined appropriately depending on the electrical and optical properties of 9, but in the case of impurities in group 1 of the periodic table, 3XlO-2 to 4 atoms
Doping should be done within the range of ic%,
In the case of impurities in Group V of the periodic table, 5X10'~2 a
Doping may be carried out within the range of ic% to fat.

In order to dope the above-mentioned impurities into a predetermined layer of the layers constituting the semiconductor layer 27, 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 impurities, those that are in a gaseous state at normal temperature and normal pressure or that can be easily gasified under at least layer-forming conditions or by a vaporizer are used.

Specifically, raw materials (impurity gas) for introducing such impurities include PH3 and P2H for introducing N-type impurities.
4, PF3, PF5, PCl3. AsH2,
AsF3゜AsF5, AsCl3, SbH3, Sb
F5, BiI3, while BF3 for P-type impurity introduction
．． BCI,,BBr3,B2O,,B4HIO,BS
H9, B6O,. , 86H,2, A1Cl3, etc.

Next, the method for forming the semiconductor fi27 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 5X 10'5To
rr or less, preferably 10-6 Torr or less.

When the pressure inside the deposition chamber 1 is reduced, the heater 4 is energized to heat the support 3 to a predetermined temperature. The temperature of the support at this time is preferably 50 to 150°C, more preferably 50 to 100°C.

As described above, since the support temperature is relatively low in the method of the present invention, it is not necessary to heat the support to a high temperature as in glow discharge deposition method or thermal energy deposition method. The energy consumption required for this can be saved.

Next, P'Ja-Si is placed on the thin layer electrode 22 on the support 21.
The valve 14-1.1 of the supply source 9 is filled with a raw material gas for Si supply as listed above in order to stack the layers.
B-1 and P2! ! The valves 14-2 and 18-2 of the supply source 10 in which the impurity gases of Send it inside.

At this time, the flow rate is adjusted while measuring with the corresponding flow meter 15-1.
A range of H is desirable.

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 tons or
r, preferably maintained in the range of 10-2 to ITorr.

When the raw material mixed gas is introduced into the deposition chamber 1, the optical energy generator 7 is driven to irradiate the raw material gas with optical energy.

As the light energy generating device 7, for example, a mercury lamp,
A xenon lamp, carbon dioxide laser, argon ion laser, excimer laser, or the like can be used.

An optical system (not shown) is incorporated so that the desired light energy generated by driving the light energy generating device 7 irradiates the support 2 installed in the deposition chamber 1.

The light energy can be irradiated uniformly or by selectively controlling the irradiated portion to the raw material mixed gas flowing near the support 2 disposed in the deposition chamber 1.

In this way, optical energy is imparted to the raw material gas flowing near the surface of the support 2, promoting photoexcitation and photodecomposition, and the generated substance a-3i and a trace amount of P-type impurity atoms are deposited on the support. Deposited.

Decomposition products other than a-Si 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 supplied through the gas introduction pipe 17. and P type a-8i layer 23
is formed. The layer thickness of P type a-3i is ioo~
104 people, preferably in the range of 300 to 2,000 people.

Thus, in the method of the present invention, light energy is used as excitation energy, and this light energy is
It is easy to control using an optical system so that the energy is always uniformly irradiated to a predetermined space occupied by the raw material gas to be irradiated, that is, so as to prevent uneven distribution of excitation energy. In addition, there is no effect of high-power discharge on the deposited layer in the process of formation due to the light energy itself, as observed in the glow discharge deposition method. The deposition layer continues to be formed while maintaining uniformity without causing defects. In particular, since light energy can be irradiated uniformly over a wide range, it has become possible to uniformly form a deposited layer over a large area with high precision.

Further, by selectively controlling the irradiated portion of the light energy, it is also possible to limit the portion on the support where the deposited layer is formed.

Note that the excitation and decomposition of the raw material gas by light energy in the present invention includes not only the case where the raw material gas is directly excited and decomposed by the light energy, but also the case where the light energy is absorbed by the raw material gas or the support and generates heat. This also includes cases where the light energy is converted into energy and the resulting thermal energy causes excitation and decomposition of the source gas, which is a derivative effect of light energy.

Next, valve 14-1. connected to gas supply source 9, lO.
1B-1, 14-2, and 1B-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 the exhaust device (not shown), the valve +4-1 is opened again.
．． 16-1 is opened, 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 the P-type a-3i layer 23.

Furthermore, in the same manner as in the formation of the P-type a-Si layer 23, light energy is irradiated to form a non-doped, ie, ■-type a-9.
An i-layer 24 is formed.

The layer thickness of the type (2) a-3i layer is preferably in the range of 500 to 5X]0'A, preferably 1000 to 10,000A.

Next, a gas supply source 11 in which N-type impurity gas is stored.
Open the valve 14-3.18-3 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 x doping concentration of the Si supply source gas, similar to the flow rate determination of the P-type impurity gas.

In the same manner as when forming the PMla-Si layer 23, optical energy irradiation is performed, and optical energy is applied to the Si supply raw material gas and the N-type impurity gas flowing near the surface of the support 2, thereby causing optical excitation and photodecomposition. 1 decomposition product a-S
i is deposited on the support, and a trace amount of N-type impurity atoms from the decomposition products are mixed into the deposit, resulting in N-type a-Si
Layer 25 is formed.

The thickness of the N-type a-Si layer 25 is preferably in the range of 100 to 10'A, preferably 300 to 2,000A.

In the formation of the P-type or NyJa-Si layer as described above, the raw material gas for supplying Si and the gas for introducing impurities used in the method of the present invention are irradiated with light energy as described above. Because it is easily excited and decomposed, 5 to +00
A layer formation rate as high as A/sec can be obtained.

Finally, the thin layer electrode 2B is formed on the N-type a-3i layer 25 by the same method as the thin layer electrode 22 to have the same layer thickness as the thin layer electrode 22, and the 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 the semiconductor layer of the PIN type diode device described above, a single layer or multilayer a-3i layer having desired electrical and optical characteristics can be formed. 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. .

According to the method of the present invention as described above, light energy is used as excitation energy, and by using a raw material gas that is easily excited and decomposed by the light energy, a film can be formed at a low energy level with a high film formation rate. It is possible to form an a-9i deposited layer, and the uniformity of electrical and optical properties is improved.
It is now possible to form an a-3i deposited layer with excellent quality stability. 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, it is easy to control the light energy so that it can always uniformly irradiate a predetermined space occupied by the raw material gas to be irradiated, and even thick deposited layers can be formed uniformly with high precision. In particular, since it can be irradiated uniformly over a wide area, it has become possible to uniformly form a deposited layer over a large area with high precision.

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

Example 1 Using the apparatus shown in FIG. 1, using the silicon compound acid 4 mentioned above as the raw material for supplying Si, and using B2H6 as the gas for introducing P-type impurities, P atoms were prepared by topping P atoms. Formation of type a-8ifi was carried out as follows.

First, the support 2 (Corning 97059, transparent conductive film (polyester base) is placed on the support 3 in the deposition chamber l.
The pressure inside the deposition chamber 1 was reduced to 104 Torr by an exhaust device (not shown) through a gas exhaust pipe 20, the heater 4 was energized to maintain the support temperature at 30° C., and then silicon compound acid 4 was filled. Valve 14 of raw material supply source 9
-1.18-1 and diluted with H2 (dilution rate 0.02
The valves -2 and 16-2 of the raw material supply source 10 filled with the P-type impurity introducing gas B2H6 (5 mol %) were opened, and the raw material mixed gas was introduced into the deposition chamber 1.

At this time, the corresponding flow meters 15-1 and 15-2 measured 17 to 82H with a gas consisting of a silicon compound positive 4.
, gas is B/Si= 5X10-3 mol/mol
The mixed gas is mixed at a ratio of 15O5, and the flow rate of the mixed gas is 15O5.
Each flow rate was adjusted to achieve CCN, the pressure inside the deposition chamber was kept at 0.1 Tart, and the light intensity was set at 200.
mW/ctn' high-pressure mercury lamp light is generated from the light energy generator 7 and irradiated perpendicularly to the support to form a P-type a-3i layer (B atom content: 5 x 10°) with a layer thickness of 400A.
3 atomic,%), 20 A/sec (7
) was deposited on support 2 at a film formation rate. Note that the light energy was uniformly applied to the gas flowing in the vicinity of the entire support body 2 disposed in the deposition chamber 1. At this time.

Decomposition products other than a-3i and B atoms and undecomposed surplus raw material gas were discharged through the gas exhaust pipe 20, while new raw material mixed gas was continuously supplied through the gas introduction pipe 17.

The a-S thus formed by the method of the present invention
For evaluation of the i-layer, a comb-shaped A1 gap electrode (length 25
The dark current was measured by measuring the dark current and calculating the dark conductivity σd.

Note that the gap electrode is a
- Place the Si layer in a vapor deposition tank and heat the nuclide once to 10゛6 Tor.
After reducing the pressure to a vacuum level of r, the vacuum level is reduced to lO''5 Torr.
The deposition rate was adjusted to 20 A/sec, 1500 A (
7) AI was deposited on the a-Si layer to a certain thickness and etched using a pattern mask having a predetermined shape.

The obtained dark conductivity σd is shown in Table 1.

Examples 2 to 5 The silicon compounds N66, #6.10, a613, and Sui 20 (Examples 2 to 5) listed above were used as raw materials for supplying Si.
P type a-
Example 1
It was measured in the same manner. The measurement results are shown in Table 1.

Comparative Example 1 A P-type a-3i layer was formed in the same manner as in Example 5 except that Si2H6 was used as the raw material for a-3i supply, and the σd of the obtained a-Si layer was made in the same manner as in Example 1. It was measured using The measurement results are shown in Table 1.

Example 6 N-type impurity introduction gas PH diluted with H2 (dilution rate 0.05 mol%) instead of BZH6 gas supply source 9
3 is used, and the flow rate of PH3 gas is such that the mixing ratio of the PH3 and the gas consisting of silicon compound 4 is P/Si layer 5X 10' mol
/Peng01, and the flow rate of these mixed gases is 15
A-S doped with P atoms, which are N-type impurities, was prepared in the same manner as in Example 1 except that the adjustment was made to obtain 03CCM.
An i-layer (layer thickness: 4000 people) was formed. Formed N-type a
A comb-shaped A1 gap electrode was also provided on the -Si layer in the same manner as in Example 1, and the dark conductivity σd was determined.

The obtained values are shown in Table 2.

Examples 7 to 10 As a raw material for supplying Si, silicon compound N66,
N-type, S-type, N was formed, and the σd of the obtained a-Si layer was measured in the same manner as in Example 1. The measurement results are shown in Table 2.

Comparative Example 2 An N-type a-9i layer was formed in the same manner as in Example 10 except that 5i2)16 was used as the raw material for Si supply, and the σd of the obtained a-3i layer was made in the same manner as in Example 1. It was measured using The measurement results are shown in Table 2.

To summarize the results of Examples 1 to 10 and Comparative Examples 1 and 2 above, as for the film formation rate, as shown in the evaluation results in Tables 1 and 2, the film formation speed in Comparative Examples 1 and 2 was is 1
Whereas it is 2A/sec.

Example 5 of the present invention, film formation rate in 1O is 28A/s
Example 1 of the present invention in which a good film formation rate with ec was obtained and
-10, sufficient doping efficiency was obtained and an a-3i layer having a high dark conductivity σd was formed.

Example 11 Using the apparatus shown in FIG. 1, using the silicon compound Su3 mentioned above as the raw material N for supplying Si, and using light from a high-pressure mercury lamp with a light intensity of 150 mW/crn' as excitation energy. Then, the support temperature was set at 40 DEG C., and a PIN type diode device as shown in FIG. 2 was formed 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, and using the same operating conditions as in Example 1, the raw material supply source 9 and 1O From there, a silicon compound, B2H, and gas were introduced into the deposition chamber 1 to form a P-type a-3i layer 23.

Next, when the thickness of the P-type a-3i layer 23 reaches 4008, the valve 14-1 connected to the gas supply source 9 and lO
．． 18-1.14-2.16-2 are all closed, and the deposition chamber l
Stop introducing gas into the room. After the gas in the deposition chamber is removed by driving the exhaust device (not shown), the valve 14-
1. Open 111-1 and add Si supply silicon compound Mf.
150 SCC of raw material gas consisting of L3 in the deposition chamber l
It was introduced at a flow rate of M.

Furthermore, Py! ! Light energy irradiation was performed in the same manner as in the formation of the 1a-3i layer 23, and the non-doped, ie, engineering type, a-3iFt24 (thickness, 5000A) was converted into a P-type a-9.
It was formed at the same speed as when the i-layer 23 was formed.

Next, open the valve 14-3. PH3 gas was introduced into the N-type a-3i layer 25 doped with P atoms using the operating conditions in Example 6.
(F! thickness 400A) was deposited on the I-type a-Si layer 24 at the same speed as in the formation of the PyJa-3i layer 23 to create a semiconductor layer 27 consisting of three a-3i layers 23, 24, and 25. did.

The PIN thus formed by the method of the present invention
A film with a thickness of 1000A (
7) AI thin film electrodes 26 were stacked to complete a PIN type diode device.

The rectification characteristics (ratio of forward current and reverse current at voltage IV), n value (current equation of P-N junction J = J (n value at exp(eV/nkT)-1)) and light irradiation characteristics (light irradiation intensity of 100 mW/c
The conversion efficiency in m2, open circuit voltage, and short circuit current were evaluated. The results are shown in Table 3.

Examples 12 to 15 As raw materials for supplying Si, the silicon compounds listed above were used. /120 (actual ju112
- 15) were used individually and the support temperature was set to the temperature shown in Table 3, but in the same manner as in Example 11.
A PIN type a-Si semiconductor layer having a layered structure was formed to produce a PIN type diode device, and the rectification characteristics, n value, and light irradiation characteristics were evaluated in the same manner as in Example 11. The results are shown in Table 3.

Comparative Example 3 A 3M structure PIN fia-9 was prepared in the same manner as in Example 15 except that Si2H6 was used as the raw material for supplying Si.
An i-semiconductor layer was formed and a PIN-type diode device was fabricated.The rectification characteristics, n-value, and light irradiation characteristics of the fabricated PIN-type diode device were evaluated in the same manner as in Example 11. The results are shown in Table 3.

Examples 16 to 20 Instead of a high-pressure mercury lamp with a light intensity of 150 mW/crn', an ArF excimer laser with a wavelength of 193■■ and a light intensity of 201J/Hulse was used, except that the support temperature was set as shown in Table 4. A PIN type a-3i semiconductor layer with a three-layer structure was formed in the same manner as in Examples 11 to 15 (Examples IS to 20) to form a PIN type D diode device, and in the same manner as in Example 11. The rectification characteristics, n value, and light irradiation characteristics were evaluated. The results are shown in Table 4.

Comparative Example 4 Three-layered PIN y! 1 la
A -Si semiconductor layer was formed to form a PIN type diode device.The rectification characteristics, n value, and light irradiation characteristics of the PIN type diode device were evaluated in the same manner as in Example 11. The results are shown in Table 4.

To summarize the results of Examples 11 to 20 and Comparative Examples 3 and 4, the PINs formed in Examples 11 to 20
The mold diode device current ratio is 8X108~8
A good rectification ratio of X 109 is obtained, and the conversion efficiency is 8%.
Above, open circuit voltage 0.8v, short circuit current 13mA/C■2
Good light irradiation characteristics 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 table 4: Heater 5: Conductor 6-1.8-2.6-3: Gas flow 7: Light energy generator 8: Light energy 9, 10, 11 .12 + Gas supply source 13-1.13-2.13-3.13-4.18: Pressure meter 14-1.14-2.14-3.14-4゜1B-1, 16-2, 16-3, 16-4, 29: Valve 15-1.15-2.15-3.15-4: Flow meter 17, 17-1, 17-2, l 7-3
, 17-4: Gas inlet pipe stirring; 20: Gas exhaust pipe 22.28: Thin film electrode 23: P type a-5i layer 24: ■
Type a-5iM25: N-type a-Si layer 27; semiconductor layer
28: Conductor ll No. 2 Figure Procedural Amendment (Own ship July 18, 1985 Commissioner of the Patent Office 1, Indication of the case 1975 Patent Application No. 78133 2, Title of invention Method for forming deposited film 3, Amendment Patent applicant (100) Canon Co., Ltd. 4, Agent Address: 1-9-20-5 Akasaka, Minato-ku, Tokyo, Claims column of the specification to be amended and the claims of the invention Detailed explanation column. 6. Contents of amendment l) The scope of claims is amended as shown in the attached sheet. 2) Line 5 from the bottom of page 5 of the specification, line 1 from the bottom of page 6, lines 4 to 5 from page 6, lines 7 to 8 of page 14, lines 2 to 2 of page 14 In line 3 and lines 6 to 7 of the same page, the statement “in genus ■ or genus V” was changed to “in group ii or genus V.”
Correct each statement. 3) Change the description of “Genus ■” in the first line of page 20 of the specification to “
The description has been corrected to "Group ■". 4) The statement "at least" on page 6, line 3 of the specification is corrected to "at". 5) The statement "belongs to" on page 18, line 12 of the specification is corrected to "1 belongs". Claims (1) In the deposition chamber in which the support is placed, the following general formula; (n is an integer from 1 to 11) and a compound containing an atom belonging to ml or vl of the periodic table, and these compounds are exposed to light energy. A method for forming a deposited film, characterized in that a deposited film containing silicon atoms and atoms belonging to group ml or group V of the periodic table is formed on the support by excitation and decomposition.

Claims (1)

[Claims] (+) In the deposition chamber in which the support is placed, the following general formula; A gaseous atmosphere is formed between a silicon compound represented by an integer from 1 to 7 (n is an integer from 1 to 11) and a compound containing an atom belonging to group M or group II of the periodic table. , a deposited film containing silicon atoms and atoms belonging to group Ⅰ or group V of the periodic table is formed on the support by excitation and decomposition using light energy. How to form a film.