JPS60219731A - Forming method of deposited film - Google Patents

Abstract

PURPOSE:To form a deposited film at high forming speed, keeping high quality by a method wherein gaseous atmosphere is formed mixing cyclic silane compound, halogen compound and the compound containing atoms which fall with the III or V group. CONSTITUTION:The valves 14-1, 16-1 of the supply source 9 filled up with the gas of cyclic silane compound which is indicated by the formula [where (n) is indicated 3, 4 or 5, R is indicated H or SiH3] and the valves 14-2, 16-2 of the supply source 10 stored P type impurity are opened respectively, and then the mixed gas, which is mixed with fixed mixture ratio, is sent into a depositing chamber 1. At the same time, valves 14-5, 16-5 are opened respectively, then halogen compound is introduced to the depositing chamber 1 from supply source 29. A photo energy generator 7 is operated and also the optical energy is irradiated to stock gas.

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. The present invention relates to a method of forming a deposited film of amorphous silicon (hereinafter abbreviated as a-Si) on a predetermined support by creating an excited 1-decomposition state of a source gas by applying or using light and, if desired, heat.

Conventionally, methods for forming deposited films of a-9i include SiH4,
Alternatively, a glow discharge deposition method and a thermal energy deposition method using Si2H6 as a raw material are known. That is, these deposition methods use 5i)14 or Si2 as the raw material gas.
This is a method in which a deposited film of a-9i is formed on a support by decomposing H6 using electrical energy or thermal energy (excitation energy), and the deposited film formed is a photoconductive film, a semiconductor, an insulating M, 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 reproducible and stable conditions such as not always achieving a uniform discharge distribution state, and furthermore, the formation of bladder 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 deposited films with uniform electrical and optical characteristics, especially those having large areas or thick films, which are susceptible to defects using this method.

On the other hand, in the thermal energy deposition method, the temperature is usually 400°C.
Since such a 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-9i will be separated increases, making it difficult to obtain the desired properties.

Therefore, one way to solve these problems is to
Recently, an a-Si optical energy deposition method (photoCVD) using SiH, Si2H6 as a raw material has been attracting 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 deposited films of a-9i to be performed at low energy levels. Ta. 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, stable reproducibility is obtained, and there is no need to heat the support to a high temperature, and the selectivity for the support is widened.

However, with this optical energy deposition method using SiH4,5i2)16 as a raw material, there is a limit to how much efficient decomposition can be expected. It has been pointed out that there are some drawbacks.

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 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 extensive studies, the present invention has achieved these objectives by using the following general formula as a raw material gas for forming an a-9i film that is decomposed by light energy; It was discovered and completed that this can be achieved by using a cyclic silane compound represented by (R represents H or SiH3) in a mixed state with a halogen compound.

That is, in the deposited film forming method of the present invention, in the deposition chamber in which the support is arranged, the following general formula;
A gaseous atmosphere is formed between a cyclic silane compound and a halogen compound represented by (iH3), a halogen compound, and a compound containing an atom belonging to group I or wind V of the periodic table, and these compounds are exposed to light. The method is characterized in that a deposited film containing silicon atoms and atoms belonging to group I or wind V of the periodic table is formed on the support by excitation and decomposition using energy.

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 wind 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 a-Si used in the method of the present invention has the following general formula; (in the above formula, n is 3, 4 or 5, R is H or O
It is a cyclic silane compound represented by H3.

Examples of such cyclic silane compounds include the following.

However, such cyclic silane compounds are efficient when using light energy as excitation energy.
Excitation and decomposition cannot be obtained, and a good film formation rate cannot be obtained.

Therefore, in the method of the present invention, a halogen compound is mixed with the cyclic silane compound in order to more efficiently promote the excitation and decomposition of the cyclic silane compound by light energy.

The halogen compound mixed with the cyclic silane compound in the method of the present invention is a compound containing a halogen atom, and can more efficiently promote excitation and decomposition of the cyclic silane compound by light energy. It is something. Such halogen compounds include CI2, B
Examples include halogen gases such as r2, I2, and F7.

The proportion of the halogen compound mixed in the raw material compound for supplying Si in the method of the present invention or the a-3i used
Although it varies depending on the raw materials for film formation and the type of halogen compound, 0.01 VoL$~e5V.

I! , preferably 0. I Volg, used within the range of ~50 VOI$.

In addition, in the cyclic silane compound represented by the above general formula, n is 6.
The above substances, in a mixed state with a halogen compound,
It is expected that the desired deposited film can be obtained by easy decomposition and low-energy excitation, but contrary to expectations, the quality of the photoconductive film and semiconductor film is poor, and in addition, defects on the surface of the film and the deposited film It was found that there was a lot of turbulence within the film, resulting in an uneven film. Therefore, if such a cyclic silane compound is used, it is difficult to control the production of the deposited film. Further, when n in the above formula is 2, it is also considered as a cyclic silane compound, but this compound is unstable and therefore difficult to isolate at present.

Therefore, n in the binary formula is preferably 3.4 or 5.

For example, B is present in the deposited film formed by the method of the present invention.
, ^1. The raw materials used to introduce atoms belonging to Group IV of the periodic table, such as Ga, In, and TI, or Group V, such as N, P, As, Sb, and Bi, contain these atoms and have a light energy easily excited by 1
Compounds that are decomposed are used, such as PH3, P2H, PF3. PF5, PC
l3. AsH3, AsF3, AsF5, AsCh,
SbH3, SbF5.86HIO, 86HI2,
AIC:13 etc. can be mentioned.

In the method of the present invention, a silicon compound as described above in a gaseous state, a halogen compound, and a compound containing an atom belonging to Group M or Group V of the periodic table are introduced into a deposition chamber, and these compounds are are irradiated with light energy to excite and decompose these, and deposit Il! containing silicon atoms and atoms belonging to group Ⅰ or w4V of the periodic table on a support placed in the deposition chamber. (a-3i 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, visible light, X-rays, -γ rays, etc., and can be appropriately selected depending on compatibility with the raw material gas.

Currently, I am releasing ML Garden to the public and explaining it to 10 million 1000-year-old publishers.

FIG. 1 shows a photoconductive film made of a-5i 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 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 17 for introducing the raw material gas for forming the a-9i film and gases such as a carrier gas used as necessary into the deposition chamber l, and a gas introduction pipe for introducing the halogen compound. tube 30
is connected to the deposition chamber l. The other end of the gas introduction pipe 17 is connected to a gas supply source 9.10, Il, 12 for supplying the raw material compound for forming the a-3i film and gases such as carrier scum used as necessary. Gas introduction pipe 30
The other end is connected to a gas supply source 29 for supplying a halogen compound.

In this way, it is preferable that the raw materials for forming the a-9i film and the halogen compound are separately introduced into the deposition chamber l. reacted at the same time as they were mixed,
This is not preferable because the raw material for forming a-5ill is decomposed and the decomposition products are deposited inside the gas introduction pipe and contaminate the inside of the gas introduction pipe.

In order to measure the flow rate of each gas flowing out towards the deposition chamber 1 from the gas supply sources 9.1O111, 12, 28, a corresponding flow meter 15-1.15-2.15-3°1 is used.
5-4. Branched gas introduction pipe corresponding to 15-5 +7-
1゜17-2.17-3.17-4 and gas introduction pipe 30
It is located in the middle of. Valve low 1.14-2.14-3.14-4.14-5 before and after each flow meter
, 16-1.18-2゜18-3.16-4.16-
5 are provided and by adjusting these valves,
A predetermined flow rate of gas can be supplied. 13-1.13-2
．． 13-3.13-4.13-5 is a pressure meter,
This is for measuring the pressure on the high pressure side of the corresponding flow meter.

Each gas that has passed through the flow meter is introduced into the deposition chamber 1 under reduced pressure by an exhaust device (not shown). Note that the pressure meter 18 measures the total pressure of the mixed gas when it flows inside the gas introduction pipe 17.

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 l is not made of a transparent material such as quartz glass, a window for irradiating the light energy 8 may be provided.

In the present invention, the source of waste 13.10, 11, 12
, 211 may be increased or decreased as appropriate.

That is, when using a single raw material gas, one gas supply source from 9 to 12 is sufficient. However, when using a mixture of two or more raw material gases, or when mixing a single raw material gas, two or more are required.

Note that since there are raw materials for forming the a-9i film and halogenated materials, a vaporization device (not shown) is installed when the raw materials are used as a liquid. Vaporizers include those that utilize heating conditions and those that pass a carrier gas through a liquid. 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.
The a-3i deposited film forming method of the present invention will be explained in more detail using an example of a method for forming a NyJ diode device.

FIG. 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, and 24 is 1-type ci') a-S+! , 25 is an N-type a-5i layer.

27 is a semiconductor layer, and 28 is a conductive wire. The support 21 is semiconductive, preferably electrically insulating. As a semiconductive support, for example, Si.

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. Ru.

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 made of 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 supports as well.

The thin film electrode 22 is made of, for example, NiCr, AI, Or,
No, Au.

Ir, Nb, Ta, V, Ti, Pt, Pd
, In2O3, 5n02. ITO (In2O3+ 5n
It can be obtained by providing a thin film such as 02) 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', more preferably 100 to 5 x 10'.

In order to make a predetermined layer among the layers constituting the semiconductor layer 27 of 8-81 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.

Py! doped into the semiconductor layer! J! Impurities include atoms belonging to Group Ⅰ of the periodic table, among which, for example,
Preferred examples include B, AI, Ga, In, TI, etc., and examples of N-type impurities include p14 of the periodic table.
Atoms belonging to group v, especially N, P, ^S, Sb
, Bi, etc. are mentioned as suitable ones, but especially B, Bi, etc.
Ga, P, Sb, etc. are optimal.

In the present invention, in order to impart a desired conductivity type, the semiconductor layer 2 is
The size of the impurity to be doped into 7 is determined as appropriate depending on the desired electrical and optical properties, but in the case of impurities in group Ⅰ of the periodic table, it is 3 x 10゛2 to 4 at. i
It is sufficient to dope the doping so that it is in the range of c%, and in the case of impurities in Group V of the periodic table, it is 5X10-' to 2 a
Doping may be done within a range of tomic%.

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, the raw material (impurity gas) for introducing such impurities is PH3, ρ2H for introducing N-type impurities.
4, PF3, PF5, PCl3. ASH3,A
sF3, A! IFs, AsCl3, SbH3,
SbF5, BiH3, while B for introducing P-type impurities
F3.8CI3, BBr3, B2H6, B, H,. , B
, H9, B6H1°, B6)(+2), AlCl3, etc.

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 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' 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, in order to stack a P-type a-Si layer on the thin layer electrode 22 on the support 21, the valve 14-1 of the supply source 9 is filled with the raw material gas for Si supply as listed above. .1B
-1 and a supply source 10 in which P-type impurity gas is stored.
17) Valve 14-2. +6-2 are opened respectively, and a mixed gas in which the source gas for supplying Si and the P-type impurity gas are mixed at a predetermined mixing ratio is sent into the deposition chamber 1. At the same time, the valves 14-5 and 18-5 are respectively opened. Open.

A halogen compound is introduced into the deposition chamber 1 from a supply source 28 .

At this time, the corresponding flow meter 15-1.15-2.1
The flow rate of the raw material gas for Si supply, which is adjusted while being measured in step 5-5, is 10-1000 S00M, preferably 20~
A range of 500 SCCH is desirable.

Further, the flow rate of the halogen compound gas is determined so that it is mixed with the Si supply raw material gas at a predetermined ratio.

The flow rate of P-type impurity gas is the flow rate of Si supply raw material gas ×
Determined from 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 1O゛2 to 100 Torr.
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 in the vicinity of 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 a-Si as a product and a trace amount of P-type impurity atoms are deposited on the support. Deposited.

Decomposition products other than a-3i and P-type impurity atoms, undecomposed surplus raw material gas, etc. are discharged through the gas exhaust pipe 20, while new raw material mixed gas is continuously supplied through the gas introduction pipes 17 and 30. is supplied to P-type a-S
i! 23 is formed. The layer thickness of P-type a-Si is 100 to 104A, preferably 300 to 2.00OA.
A range of is desirable.

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. Yes, and also by the light energy itself. There is no effect of high-power discharge on the deposited layer during the formation process, as observed in the glow discharge deposition method, and uniformity can be maintained without disturbing the layer surface during deposition or causing defects within the deposited layer. The formation of the deposited layer continues while maintaining the temperature. 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 possible to limit the portion where the deposited layer is formed with the support.

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 light energy.

This also includes cases where the light energy is absorbed by the raw material gas or the support and converted into thermal energy, and the resulting thermal energy causes the excitation and decomposition of the raw material gas due to a derivative effect of the light energy. - then a valve 14 connected to the gas supply 9.10.28;
-1.18-1.14-2.16-2.14-5.1B
-5 are all closed to stop the introduction of gas into the deposition chamber l.

After the gas in the deposition chamber is removed by driving an exhaust device (not shown), the valve 14-1.18-1.14-5.1 is opened again.
6-5 is opened, and the raw material gas for supplying Si is introduced into the deposition chamber 1.

In this case, the preferred flow conditions and pressure conditions are P-type a-Si
The conditions are the same as those used when forming layer 23.

Furthermore, in the same manner as in the formation of the Pfia-Si layer 23, optical energy is irradiated to form a non-doped, ie, type 1 a-
A 3i layer 24 is formed.

The layer thickness of type (2) a-5il is 500-5XIO'A, preferably 1000-10. GOOA range is preferred.

Next, a gas supply source 11 in which N-type impurity gas is stored.
Pulp +4-3 connected to 18-3 and depositing chamber l
An N-type impurity gas is introduced into the chamber.

The flow rate of the N-type impurity gas is determined from 51 the flow rate of the supply source gas x the doping concentration, as in the case of determining the flow rate of the P-type impurity gas.

In the same manner as when forming the P-type a-Si layer 23, optical energy irradiation is performed, and optical energy is applied to the Si supply source gas, the halogen compound gas, and the N-type impurity gas flowing near the surface of the support 2. , photoexcitation and photolysis are promoted 1
The a-9i decomposition products are deposited on the support, and a trace amount of N-type impurity atoms of the decomposition products are mixed into the deposit, thereby forming the N-type a-5i layer 25.

The layer thickness of the N type (F) a-3i layer 25 is 100-10'A
, preferably in the range of 300 to 2,000 OOA.

In the formation of the P-type and N-type a-3i calendars as described above, the raw material gas for supplying Si and the gas for introducing impurities mixed with the halogen compound used in the method of the present invention are as described above. As mentioned above, since it is easily excited and decomposed by light energy, a layer formation rate of about 5 to 100 A/sec can be obtained.

Finally, a thin layer electrode 26 is formed on the N type a-9i 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 the semiconductor layer of the PIN type diode device described above, it is also possible to form a d-5i layer consisting of an intermediate layer or multiple layers having desired electrical and optical characteristics. can be formed. Further, in the example 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 may be performed under normal pressure or increased pressure as desired. can.

According to the method of the present invention as described above, optical energy is used as excitation energy, and a halogen compound is mixed with a cyclic silane compound, which is a raw material for supplying Si for forming an a-9i film. The formula silane compound is efficiently and easily excited and decomposed by light energy, making it possible to form an a-3i deposited layer at a low energy level with a high deposition rate, resulting in uniform electrical and optical properties and stable quality. It became possible to form an a-9i deposited layer with excellent properties. 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 irradiate uniformly over a wide area, it is possible to uniformly form a deposited layer over a large area with high precision.
'I became a Noh.

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

Example 1 Using the apparatus shown in FIG. 1, the above-mentioned silane compound 1 was used as the raw material for supplying S1, I2 was used as the halogen compound, and B2H,
A P-type a-3i layer doped with P atoms was formed using the following method.

First, a support (polyethylene terephthalate) is set on the support stand 3 in the deposition chamber 1, and the interior of the deposition chamber 1 is heated to 10' Torr by an exhaust device (not shown) through the gas exhaust pipe 20.
The pressure is reduced to r, and the heater 4 is energized to raise the support temperature to 80°C.
Then, the valves 14-1.18-1 and 14-5 of the raw material supply source 9 filled with silane compound No. 1 and I2 are roughly diluted with H2. (ioooppm H2 dilution) P-type impurity introduction waste B2 Raw material supply source filled with Hb 1O
The valves 14-2 and 16-2 were each opened, and the raw material mixed gas was introduced into the deposition chamber 1.

At this time, the corresponding flow meter +5-1.15-2゜1
If the silane compound is not measured at 5-5, the l will be +50SC.
The flow rates of CM Ni and t f-PH3i were adjusted to 40 SCCH, and the flow rate of I2 was adjusted to 30 SCCH.

Next, the pressure in the deposition chamber was maintained at Q, l Torr, and cannon light with a light intensity of 130 mW/crn' was generated from the optical energy generator 7 and irradiated perpendicularly to the support.
P-type δ-Si layer 3 with a layer thickness of 400A (B atom content 5
X 10' atomic,%), 50A/sec
The film was deposited on the support 2 at a film formation rate of . Note that the light energy was uniformly applied to the gas flowing in the vicinity of the entire support 2 disposed in the deposition chamber 1. At this time,
Decomposition products other than a-3i and B atoms, undecomposed surplus raw material gas, etc. are exhausted through the gas exhaust 'Ft' 20, while new raw material mixed gas is continuously supplied through the gas introduction pipes 17 and 30. Supplied.

a-3 thus formed by the method of the present invention.
For evaluation of the i-layer, a comb-shaped AI 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 thin coating tank and conduct a microscopic examination at 104 Torr.
After reducing the pressure to a vacuum degree of A pattern mask was formed by etching using a pattern mask.

The obtained dark conductivity σd is shown in Table 1.

Examples 2 and 3 As a halogen compound, 5rz (Example 2) or Cl
Formation of type I a-SiM was carried out in the same manner as in Example 1 except that 2 (Example 3) was used, and the obtained a-5il
i was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Examples 4 to 12 As the raw material for forming a-3itti laminated film and the /\rogen compound, the above-mentioned silane compounds were used.
and I2. A-9il151 was deposited in the same manner as in Example 1, except that each of Br2 and CI2 was used in combination and the support temperature and /\ rogen gas flow rate were set as shown in Tables 1 and 2. . The obtained a-Si film was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

The silane compound No. 1 described above as a raw material for relatively 1 to 4 a-3i supply.
, 1. No, 2. + to 11, 3. a-SiM was deposited in the same manner as in Example 1 except that No. 4 was used, the support temperature was set as shown in Tables 1 and 2, and no halogen compound was used. The obtained a-9i film was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Examples 13 to 24 a-3i As the raw material for supply and the halogen compound, the silane compound described above, 1. It+, 2, positive, 3, positive, 4 and I2, Br2, CI2 were used in individual combinations, N-type P)13 was used as the impurity introducing gas, and the support temperature and/or ＼Table 3 for rogen gas flow rate
An a-Si film was deposited in the same manner as in Example 1 except that the settings were as shown in Table 4.

The obtained a-SiM was evaluated in the same manner as in Example 1.

The evaluation results are shown in Tables 3 and 4.

Comparatively 5-8 a-5i The silane compound described above as a raw material for forming a deposited film, 1. No. 2, No. 3, No. 4 was used, the support temperature was set as shown in Tables 3 and 4, no halogen compound was used, and N-type PH3 was used as the impurity introduction gas. θ-5il! was used in the same manner as in Example 1 except that θ-5il! J was deposited. The obtained a-Si film was evaluated in the same manner as in Example 1. The VI value results are shown in Tables 3 and 4.

Comparing corresponding examples using the same type of a-9iIll source, it was found that when a halogen compound was mixed, the film-forming rate was about 2 to 6 times higher when doped with B and H6 than when it was not mixed. When P)13 was doped, the film formation rate increased by about 2 to lθ times. The rate of acceleration of film formation rate depending on the type of halogen is generally C10
, Br2, and I2 increased in this order, and the electrical characteristics also became better.

Example 25 Using the apparatus shown in FIG. 1, using the above-described silane compound No. 1 as a raw material for supplying Si, and using cannon light with a light intensity of 130 W/crrr' as excitation energy, PIN type diode as shown in Figure 2.
The device was formed as follows.

First, the support 21 (ITO (Indiui+Tin)
A polyethylene naphthalate transparent conductive film with 100 OA of vapor-deposited
and using the same operating conditions as in Example 1, silane compounds No. 1, B were obtained from raw material sources 9 and 28.
2H6 gas and I2 gas are introduced into the deposition chamber 1 to form a P-type a
-Si layer 23 was formed.

Next, when the thickness of the P-type a-5i layer 23 reaches 40 OA, the valves 14-1.18-1.14-2. connected to the gas supply sources 9, ]0 and 29. H5-2, 14-5
, 18-5 are all closed, and the introduction of gas into the deposition chamber 1 is stopped. After the gas in the deposition chamber is removed by driving the exhaust device (not shown), the valve +4-1.16-1.14- is opened again.
5. Open lff-5 and insert silicon supply silica 7 Compound 1
b, 1 wo150SCCM, I.

Gas was introduced into the deposition chamber 1 at a flow rate of 30 SCCM.

Furthermore, in the same manner as in the formation of the P-type a-Si layer 23, light energy irradiation is performed to form a non-doped, i.e., ■-type a-5i layer.
Layer 24 (layer thickness, 5000 A) was formed at the same speed as when P-type a-Si layer 23 was formed.

Next, the valve 14-3.16-3 connected to the gas supply source 11 in which the N-type impurity introduction gas PH3 diluted with H2 (dilution rate 0.05 mol%) is stored is opened, and the inside of the deposition chamber 1 is opened. PH3 gas was introduced into the N-type a-3i layer 2 doped with P atoms using the operating conditions in Example 13.
5 (N thickness 400A) was deposited on the I-type a-9i layer 24 at the same speed as when forming the Pfia-Si layer 23 to create a semiconductor layer 27 consisting of three a-3i layers 23, 24, and 25. did.

Thus formed by the method of the present invention. P.I.
An AI thin film electrode with a thickness of 1000 Å was further applied on the N-type a-3i semiconductor layer 27 using a vacuum evaporation method (pressure I x 10' Torr) to complete a PIN type diode device.

The rectification characteristics (ratio of forward current and reverse current at voltage l) of the PIN type diode device (area 1 ctn') formed in this example, the n value (current equation of P-N junction J = J (exp(eV/nkT)-!n value at 1) was evaluated.The results are shown in Table 5.
Shown below.

Examples 26 to 36 a-3i As the supply gas and the halogen compound, the above-mentioned silane compounds No. 1. altt, 2.11+,
3 and I2. Br2. A three-layer PINfia-3i semiconductor layer was prepared in the same manner as in Example 25, except that each of C12 was used in combination and the support temperature and halogen gas flow rate were set as shown in Tables 5 and 6. The 0 created PIN! formed a PIN type diode device. ! ! The rectification characteristics, n value, and light irradiation characteristics of the diode device were evaluated in the same manner as in Example 25. The results are shown in Tables 5 and 6.

Comparative Example 9 - 2 a-5i The above-mentioned silane compound was used as the supply gas for the deposited film, 1. A three-layer structure was prepared in the same manner as in Example 25 except that Nb, 2, 3, and 4 were used, the support temperature was set as shown in Tables 5 and 6, and no halogen compound was used. Form a PIN type a-9i semiconductor layer of
9 Created PI that created an N-type diode device
The rectification characteristics, n value, and light irradiation characteristics of the N-type diode device were evaluated in the same manner as in Example 25. The results are shown in Tables 5 and 6.

To summarize the results of Examples 25 to 36 and Comparative Examples 9 to 12 above, the PINs formed in Examples 25 to 36
The rectifying properties of the type diode devices were better with halogen gas than without when using a homogeneous a-Si feed gas at low support temperatures of 50-100°C.

Table 1 Dark conductivity when using 1I B2H6 as a doping gas (October 1) -1 Table 2 Dark conductivity when using $I B2)+6 as a doping gas (Ω・C■), t , room temperature table 3 12 Dark conductivity (Ω・C ■) when using 13 as a doping gas Table 4 Dark conductivity (Ω-C layer) when using 22 PH as a doping gas 1 Table 5 Book 3 Ratio of forward current and reverse current at voltage IV (table in logarithm) Current formula of zero 4p-n junction J=”(eXp(”’
n value (Quality fact
or) Table 6 3. n value (Quality factor) in the ratio of forward current and reverse current at voltage iv

[Brief explanation of the drawing]

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 6-1.8-2.8-3.6-4: Gas flow 7: Light energy generator 8 Two light energy 8 , +0.11, 12.29: gas supply source 13-1.
13-2.13-343-4.13-5.18: Pressure meter 14-1.14-2.14-3.14-4.14
-5゜1B-1, 18-2, lff-3, 113-4,
18-5, 31: Valve 15-1.15-2.15-3
．． 15-4.15-5: Flow meter 17.17-
1j7-2j7-3.17-4.30: Gas introduction pipe 2
0: Gas exhaust pipe 22. 28: Thin film electrode 23: P type 6-S i FJ
24: I-type a-9i layer 25: N-type a-5i calendar 27: Semiconductor layer 28: Conductor procedure amendment (voluntary) August 11, 1980 Commissioner of the Japan Patent Office, Indication of case 1988 Patent application No.? fi129
2. Name of the invention Method for forming a deposited film 3. Relationship with the person making the amendment Patent applicant (100) Canon Co., Ltd. 4 Agent address 1-9-20-5 Akasaka, Minato-ku, Tokyo; Target drawing. 6. Details of the amendments are as shown in the attached sheet. ll Figure 2 Procedural Amendment (Voluntary) July 16, 1980 Commissioner of the Patent Office 1, Indication of Case 1980 Patent Application No. 761211
No. 2, Name of the invention Method for forming a deposited film 3, Relationship with the case of the person making the amendment Patent applicant (100) Canon Co., Ltd. 4 Agent address 1-9-20-5 Akasaka, Minato-ku, Tokyo Amendment Claims column and Detailed Description of the Invention column of the subject specification. 6. Contents of the amendment l) The scope of the claims will be amended as shown in the attached sheet. 2) In the 4th line to 3rd line from the bottom of page 5 of the specification, “
``A cyclic silane compound and a halogen compound.''
The statement “with a cyclic silane compound” has been corrected. 3) Line 2 from the bottom of page 5 of the specification, line 3 of page 6, lines 6 to 7 of the same page, lines 9 to 10 of the same page, line 5 of page 10, and line 5 of the same page In line 9, the statement "In genus M or V" is corrected to "In group II or V." 4) The description of "Genus ■" on page 9, line 13 and page 1B, line 15 of the specification is corrected to the description of "group ■." 5) Change the description of “Genus V” on page 9, line 14 of the specification to “
The description has been corrected to "Group V". 6) The statement "belongs to" on page 18, line 6 of the specification is corrected to "belongs to". Claims (1) In the deposition chamber in which the support is placed, the following general formula; (However, in the above formula, n is 3.4 or 5, R is H or S
A gaseous atmosphere is formed between a cyclic silane compound L halogen compound represented by iH3) and a compound containing an atom belonging to sm1 or VM of the periodic table, and these compounds are heated using light energy. A method for forming a salt 81 film, 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 excitation and decomposition.

Claims (1)

[Claims] (1) In a deposition chamber in which a support is placed, a cyclic silane compound and a halogen compound represented by the following general formula; , by forming a gaseous atmosphere of a halogen compound and a compound containing atoms belonging to Group Ⅰ or Group V of the periodic table, and exciting and decomposing these compounds using light energy. 1. A method for forming a deposited film, comprising forming a deposited film containing silicon atoms and atoms belonging to Group M or Group V of the periodic table on a body.