JPS60219733A - Forming method of deposited film - Google Patents

Abstract

PURPOSE:To uniformalize and stabilize electrical and optical characteristics by a method wherein the gaseous atomosphere of chained slane compound indicated by SinH2n+2, halogen compound and the compound which contained atoms falled with the III or V group is formed. CONSTITUTION:The valves 14-1, 16-1 of the supply source 9 filled with the gas of chained silane compound with a side chain indicated SinH2n+2 (n>=4), and the valves 14-2, 16-2 of the supply source 10 storing P type impurity are opened respectively, and then mixed gas is sent into a depositing chamber 1. At the same time, valves 14-5, 16-5 are opened respectively, halogen compound is introdued to the depositing chamber 1 from supply source 29. A photo energy generator 7 is operated and also the optical energy is irradiated to the 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 particularly relates to a method of forming a deposited film of amorphous silicon (hereinafter abbreviated as a-9i) on a predetermined support by creating an excited and decomposed state of a source gas by applying or using light and, if desired, heat.

Conventionally, methods for forming a-Si deposited films 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 SiH4 or Si2H as a raw material gas.
6 is electrical energy or thermal energy (excitation energy)
This is a method in which a deposited film of a-9i is formed on a support by decomposition, and the deposited film thus formed is used for various purposes such as a photoconductive film, a semiconductor film, or an insulating film.

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 influence of high-power discharge on the film inside is large, and it is difficult to ensure the uniformity of the electrical and optical properties of the formed film.It is difficult to ensure the stability of the quality. It has been extremely difficult to form a thick or thick deposited film with uniform electrical and optical characteristics by this method, especially one area in which defects are likely to occur.

On the other hand, in the thermal energy deposition method, the temperature is usually 40''C.
Second, the need for high temperatures limits the support materials that can be used, and in addition, increases the probability that useful bonded hydrogen atoms in the desired a-3i will separate, making it difficult to achieve the desired properties. Hard to get.

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 excitation energy instead of glow discharge or heat in the aforementioned methods, and allows the fabrication of a-9i salt 8I films to be carried out at low energy levels. became. In addition, it is easy to uniformly irradiate the source gas with light energy, and it is possible to form a high-quality 1& 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 made in view of such a problem,
An object of the present invention is to provide a light energy deposition method that uses light as excitation energy and can form a deposited film containing silicon atoms at a low energy level at a high film formation rate while maintaining high quality.

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 intensive studies, the present invention has achieved these objectives by using a chain formula having a side chain represented by the general formula: 'S:5H2o+2 (n≧4) as a raw material gas for forming δ-51M that is decomposed by light energy. It was discovered and completed that this can be achieved by using a silane compound in a mixed state with a halogen compound.

That is, in the deposited film forming method of the present invention, the general formula; 5inH2n +2 (n≧
4) A gaseous atmosphere is formed with a chain silane compound having a side chain represented by the formula, a halogen compound, and a compound containing an atom belonging to Group I or Group V of the periodic table, and these compounds are exposed to light energy. The method is characterized in that 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.

In the method of the present invention, a silicon compound obtained from the Si supply source is used as a raw material, and a compound containing these atoms for introduction of atoms belonging to Group I or Group V of the periodic table is used. The deposited film formed 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. be.

The raw material for supplying Si used in the method of the present invention is:
It is a chain silane compound having a side chain represented by the general formula: 5inH2o+z (n≧4), and is a high-quality d-3i
In order to form a deposited film, n in the above formula is 4 to 15,
Preferably 4-10. More preferably, it is 4-7.

Examples of such compounds include those represented by the following formula.

Final I SiH3-SiH-SiH3 1H3 Si)13 [Final 2 SiH3-Si -SiH3 ■ SiH3 SiH3 ! ,3SiH3-Si-5i)12-SiH3S
iH3 However, when a chain silane compound having such a side chain uses light energy as excitation energy, efficient excitation and decomposition cannot be obtained, and a good film formation rate cannot be obtained.

Therefore, in the method of the present invention, in order to more efficiently promote the excitation and decomposition of the above-mentioned chain-type silane compound having a side chain by light energy, a halogen compound is mixed into the chain-type silane compound having the side chain. be done.

In the method of the present invention, the halogen compound mixed with the chain-type silane compound having the above-mentioned side chain is a compound containing a halogen atom, and is capable of excitation and decomposition by light energy of the chain-type silane compound having the above-mentioned side chain. This can be promoted more efficiently. Examples of such halogen compounds include halogen gases such as C10, Br2, I2, and F2.

The proportion of the halogen compound mixed in the raw material compound for forming the 8-81 film in the method of the present invention or the amount of a used
-S i Itl-forming raw material compound and the type of norogen compound, etc., but 0. O1~80Vol$
.

Preferably, it is used within the range of 0.1 to 50Vo 1%.

For example, B,
Raw materials used to introduce atoms belonging to Group Ⅰ of the periodic table such as AI, Ga, In, TI, etc. or Group V such as N, P, As, Sb, Bi, etc. include these atoms, Compounds that are easily excited and decomposed by light energy are used; such compounds include:
For example, PH3, P2H,, PF3. P.F.

PCl3, ^sH3, AsF3, AsFl, AsCl3
, Sb)+3.5bF1, BiO2, BF3, 8
C13, BB T3, B2H6, B4H,. ,B,)+
9.86H,. , B6HI2, AlCl3, etc.

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 Ⅰ or MV of the periodic table are introduced into a deposition chamber, and these compounds are These are excited and decomposed by irradiation with light energy, and a deposited film (a-3i film) containing silicon atoms and atoms belonging to group Ⅰ or group V of the periodic table is formed on a support placed in the deposition chamber. It 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, and gamma rays, 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 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-3i 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. The a-SiM is placed inside the deposition chamber l.
A gas introduction pipe 17 for introducing a raw material gas for formation and a gas such as a carrier gas used as necessary, and a gas introduction pipe 30 for introducing the halogen compound.
is connected to the deposition chamber l. The other end of the gas introduction pipe 17 is connected to a gas supply source 9.1O111, 12 for supplying the raw material compound for forming the A-8T film and a gas such as a carrier gas used as necessary. tube 30
The other end is connected to a gas supply source 2S for supplying a halogen compound.

As described above, it is preferable that the raw material compound for forming the a-Si film and the halogen compound are introduced into the deposition chamber l separately. I reacted at the same time as the person was asked, and a
-3i The raw material for film formation is decomposed, and the decomposition products are deposited inside the gas introduction pipe, which is not preferable because it contaminates the inside of the gas introduction pipe.

In order to measure the flow rate of each gas flowing out from the gas supply sources 9.10, +1.12.28 towards the deposition chamber l, the corresponding ? Low meter 15-1.15-2.15-3゜1
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. There are valves 14-1.14-2.14-3.14-4.14- before and after each flow meter.
5. 18-1.16-2゜IB-3, 18-4, 16
-5 are provided, and by adjusting these valves, a predetermined flow rate of gas can be supplied. +3-1.13-
2.13-3.13-4.13-5 is a pressure meter, which is used to measure the pressure on the high pressure side of the corresponding flow meter. Each gas passing through the flow meter is It is introduced into the deposition chamber l under reduced pressure by an exhaust device. 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 gas supply source El, 10, 11, 12
．． The number of 29 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 some of the a-3ildl-forming raw material compounds and halogen compounds do not turn into gases at room temperature and remain liquids, so if they are used as liquids, 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 the 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.
Using an example of a method for forming an N-type diode device,
The a-Si deposited film forming method 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 body, 22 and 26 are thin film electrodes, 23 is a P-type a-Si layer, 24 is a 1-type (7) a-9i layer, 25 is an N-type a-9i layer, 27 is a semiconductor layer, 28 is a conductor. The support 21 is semiconductive, preferably electrically insulating. As the semiconductive support, for example, S
i.

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, N + Cr +^l, Cr
, No, Au.

Ir, Nb, Ta, v, T+, pt, pa, In2O5
+ """2+ It is obtained by providing a thin film such as ITO (In2O3+ SnO□) 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''A, more preferably 100 to 5 x 103A.

In order to make a predetermined layer among the layers constituting the semiconductor layer 27 of a-3i 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, ^S, Sb, Bi, etc. However, especially B, (ia, 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 appropriately determined depending on the desired electrical and optical properties, but in the case of impurities belonging to Group 1 of the periodic table, it is 3×1O゛2-4 atosi
All you have to do is dope it so that it falls within the range of c%, which is 1 of the periodic table! In the case of sV group impurities, 5X10'~2
Doping may be carried out within the range of atomic%.

In order to dope a predetermined layer of the semiconductor layer 27 with the above-mentioned impurities, it is sufficient to introduce a raw material for impurity introduction into the deposition chamber in a gaseous state when forming one layer. 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. AsH3,A
sF3゜AsF5, AsCl3, SbH3, SbF5
, Bi)+3, while for P-type impurity introduction BF3
, BCh, BBr*, B2O,, B, H,. , B.S.H.
9, B61(,., E&H, 2, AlCl, 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 5X10' orr.
Hereinafter, it is 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.

In addition, PfIla-S is deposited on the thin layer electrode 22 on the support 21.
In order to stack the i-layer, the valve +4-1 of the supply source 9 filled with the raw material gas for supplying Si as listed above.
18-1 and valves 14-2 and 18-2 of the supply source 10 in which the pl impurity gas is stored were opened, and the Si supply raw material gas and the P-type impurity gas were mixed at a predetermined mixing ratio. The mixed gas is sent into the deposition chamber 1, and at the same time valves 14-5 and 16-5 are opened.

A halogen compound is introduced into the deposition chamber 1 from the supply 829.

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 1O-100O300M, preferably 20-5
A range of 003CC11 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 the impurity gas at p5 is the flow rate of the raw material gas for Si supply ×
Determined from doping concentration.

However, since the amount of impurity gas to be mixed is extremely small, in order to facilitate flow rate control, the impurity gas is normally 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 10-2 to I Torrc7).

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-9i 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 noa-S
An i-layer 23 is formed. The layer thickness is 100-10'A, preferably 300-2.
A range of 00OA 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. Furthermore, the light energy itself does not affect the deposited layer in the process of formation due to high-power discharge, as observed in the glow discharge deposition method. The formation of the deposited layer continues while maintaining uniformity without causing any 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, the valve 14 connected to the gas supply source 9.1O128
-1.18-1.14-2.1B-2,14-5,18
-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 valves 14-1.1B-1, 14-5, 1 are opened again.
8-5 is opened, and the raw material gas for supplying Si is introduced into the deposition chamber 1.

In this case, the preferred flow rate and pressure conditions are P type a-3i
The conditions are the same as those used when forming layer 23.

Furthermore, in the same manner as in the formation of the P-type ♂-9i layer 23, light energy irradiation is performed to form a non-doped, that is, I-type a-3
An i-layer 24 is formed.

The layer thickness of the (2) type a-Si layer is preferably in the range of 500 to 5×10'A, preferably in the range of +000 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 N-type impurity gas is P'! As in the case of determining the flow rate of impurity gas in No. 11, it is determined from the flow rate x doping concentration of the raw material gas for supplying Si.

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,
A-Si, which is a decomposition product, is deposited on the support, and a trace amount of N-type impurity atoms from the decomposition product is mixed into the deposit, thereby forming N-type a-5i MI25.

The thickness of the Nff1 a-Si layer 25 is 100-10'A
, preferably in the range of 300 to 2,000 OOA.

In the formation of the P-type and N1a-9i layers 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. In addition, 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, the thin layer electrode 2B is formed on the N-type a-Si 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 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 the formation of the PIN type D type diode device conductor layer described above, it is possible to form a single layer or multilayer layer having desired electrical and optical characteristics. A calendar can be formed. Furthermore, 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 can be carried out under constant pressure or under pressure, as desired. You can also do it.

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 chain silane compound having a side chain, which is a raw material for supplying Si for forming a-Si film. As a result, chain-type silane compounds having side chains are efficiently and easily excited and decomposed by light energy, making it possible to form an a-Si deposited layer at a low energy level with a high deposition rate, resulting in electrical and optical It has become possible to form an a-9i deposited layer with excellent uniformity of properties and stability of product purchase. 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, the above-mentioned silane compounds No. 1 and 1 were used as raw materials for supplying Si, I2 was used as a halogen compound, and 82H6 was used as a gas for introducing P-type impurities.
A P-type a-Si 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 pumped through the gas exhaust pipe 20 by an exhaust device (not shown) for 10"' To
The pressure is reduced to rr, and the heater 4 is energized to raise the support temperature to 80
℃, then the valve 14-1.18-1 of the raw material supply s9 filled with silane compound No. 1 and the valve 14-5.18-5 of the source 29 filled with H2
Raw material supply source 10 filled with P-type impurity introducing gas B2H6 diluted by (1000 pp H2 dilution)
The valves 14-2 and 18-2 were opened, and the raw material mixed gas was introduced into the deposition chamber 1.

At this time, the corresponding flow meter 15-1.15-2゜1
5-5, silane compound No. 1 is 150
SC(:M 2, t) The flow rates were adjusted to 40SCCH2 for PHs gas and 1105CC for Zarani 2.

Next, the pressure inside the deposition chamber was reduced to 0. The PJa-9i layer 3 (B atom content 5 X
10' atomic,%), 50 A/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 body 2 disposed in the deposition chamber 1. At this time, a
Decomposition products other than -9i and B atoms, undecomposed surplus raw material gas, etc. are discharged through the gas exhaust pipe 20,
Meanwhile, new raw material mixed gas was continuously supplied through the gas introduction pipes 17 and 30.

a-3 thus formed by the method of the present invention.
Evaluation of the i-layer was performed by adding a comb-shaped AI gap electrode (length 2
The dark current was measured by forming a 50 mm (50 cm long, 5 mm wide) and calculating its dark conductivity σd.

Note that the gap electrode is a
- Place the Si layer in a vapor deposition tank, and once the nuclide is heated to 104 Torr.
After reducing the pressure to a vacuum level of
(7) layer thickness was formed by depositing AI on the a-Si layer, and etching it using a pattern mask having a predetermined shape.

The obtained dark conductivity σd is shown in Table 1.

Examples 2 and 3 As a halogen compound, Br2 (Example 2) or Cl
A type I a-3i film was formed in the same manner as in Example 1, except that Example 2 (Example 3) was used, and the obtained a-5i film was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Examples 4 to 9 The silicon compounds 11k1.2. described above were used as raw materials and halogen compounds for forming the a-3i deposited film. No. 3
, I2, Br7, and CI2 were used in combination, and an a-Si film was deposited in the same manner as in Example 1, except that the halogen gas flow rate was set as shown in Tables 1 and 2. . 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.

relatively 1-3 The compound described above is used as a raw material for supplying a-Si.

1, No, 2. A-
A 9i film was deposited. The obtained a-S;S was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2. Examples 1O to 18 As the raw materials for a-Si supply and the halogen compounds, the above-mentioned compounds 1, 1, 2, 3, I2, Br2,
The procedure was the same as in Example 1, except that C12 was used in combination individually, N-type PH3 was used as the impurity introducing gas, and the halogen gas flow rate was set as shown in Tables 3 and 4. Then, an a-3i film was deposited. Obtained a
-Sillll was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 4.

The above-mentioned silane compounds No. 1. No, 2. Using Nb, 3, /\
a-Sill was deposited in the same manner as in Example 1, except that no halogen compound was used and N-type PH3 was used as the impurity introduction gas. Obtained a-8i
The membrane was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 4.

Comparing corresponding examples using the same type of a-3i membrane source, the B2H6 doping yields approximately 2 to 3
The film formation rate increased by a factor of two, and when PH3 was doped, the film formation rate increased by about 2 to 3 times. The rate of film formation rate acceleration depending on the type of halogen is generally CI2, Br2, I
In the order of No. 2, the electrical characteristics also became better.

Example 19 Using the apparatus shown in FIG. 1, using the silicon compound +1&), 1 described above as the raw material for supplying Si, and using xenon light with a light intensity of 130 W/ctn' as the excitation energy. , the formation of a PIN type diode device as shown in FIG. 2 was carried out as follows.

First, the support 21 (ITO (Indium Tin)
A polyethylene naphthalate transparent conductive film on which 1000A of 1000A , 1. B2H
6 gas and I2 gas are introduced into the deposition chamber 1.
An 8i layer 23 was formed.

Next, when the thickness of the P-type a-Si layer 23 reaches 40OA, valves 14-1.18-1.14-2.16-2.14- are connected to the gas supply sources 9, 1O and 29. 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 14-1.18-1.14-5 is opened again.
．． Open 18-5, insert the silane compound for Si supply, and add +50 SCCM.

I2 gas was introduced into the deposition chamber 1 at a flow rate of 103 CCN.

Furthermore, in the same manner as in the formation of the P-type δ-Si layer 23, light energy is irradiated to form a non-doped, ie, I-type a-3i layer.
Layer 24 (layer thickness, 5000 A) was formed at the same speed as when P-type a-Si layer 23 was formed.

Next, a gas supply source 11 in which N-type impurity introducing gas PH3 diluted with H2 (dilution rate 0.05 mol%) is stored. Open pulp 14-3.18-3 connected to
PH3 gas was introduced into the deposition chamber 1, and the N-type a-5i layer 25 doped with P atoms (layer thickness 400A) was formed using the same operating conditions as in Example 13 as in the formation of the PyJla-3i layer 23. deposited on the type I a-3i layer 24 at a rate of 3
δ-Si! Semiconductor layer 27 consisting of 23.24.25
It was created.

The PIN thus formed by the method of the present invention
A vacuum evaporation method (pressure I
film thickness 1000A (7
) AI thin film electrodes were stacked to form a PIN type diode device.

Rectification characteristics (ratio of forward current to reverse current at voltage lV) of the PIN type diode device (area 1 crn') formed in this example, n value (current equation of P-N junction J = J (n value at exp(eV/nkτ)-1)) was evaluated. The results are shown in Table 5.

Examples 20 to 21 a-5i As the supply gas and the halogen compound, the above-mentioned silane compound Nb, 1. Nb, 2, 3 and I2, B
A three-layer PIN type a-9 was prepared in the same manner as in Example 1B except that r2 and CI2 were used in combination and the halogen gas flow rate was set as shown in Tables 5 and 6.
An i-semiconductor layer was formed and a PIN type diode device was created.The rectification characteristics, n value, and light irradiation characteristics of the manufactured PIN type diode device were evaluated in the same manner as in Example 18. The results are shown in Tables 5 and 6.
Shown below.

Comparative Examples 7 to 9 Silane compound N described above as a-3i deposited film supply gas
o, 1. 3 was prepared in the same manner as in Example 18 except that No. 2, No. 3, and no halogen compound were used.
A PIN type a-Si semiconductor layer with a layered structure was formed to form a PIN type diode device.The rectification characteristics, n value, and light irradiation characteristics of the created PIN type diode device were the same as in Example 19. It was evaluated as follows.

The results are shown in Tables 5 and 6.

Summarizing the results of Examples 18 to 27 and Comparative Examples 7 to 9 above, the flow characteristics of the PIN type diode device formed in Examples 18 to 27 are as follows at a low support temperature of 50 to 100°C. , when using a homogeneous a-9i feed gas, the use of halogen gas was better than without.

Table 1 Dark conductivity when using 2182H6 as a doping gas (Ω・0) - Table 2 11 Dark conductivity when using B2H6 as a doping gas (Ω・0) - 1 Table 3 22 Dark conductivity (Ω-C layer) when PH3 is used as a doping gas -1 Table 4 $2 Dark conductivity (Ω・C■) when PH3 is used as a doping gas -1 Table 5 House 3 Voltage 1 ■ Ratio of forward current and reverse current at (logarithm) n value (Quality factor) at front
Table 6 House 3: n value (Quality factor) in the ratio of forward current to reverse current (expressed in logarithm) at 11 voltage lv

[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 8-1.8-2.8-3.8-4: Gas flow 7: Light energy generation II 8: Light energy 8 .10, 11, 12, 211: Gas supply source 13-1
．． 13-2.13-3.13-4.13-5.18: Pressure meter 14-1.14-2.14-3.14-4.
14-5゜1B-1, 16-2, 1 [1-3, IEI-
4,18-5,31: Valve 15-1.15-2.15
-3.15-4.15-5: Flow meter 17.1
7-1.17-2.17-3.17-4.30: Gas inlet pipe 20 Gas exhaust pipe 22.28: Thin film electrode 23: P type a-3iF! t24
: Engineering type a-Si calendar 25: IjlJJa-5i layer 27
: Semiconductor M28: Conductor ll Figure 2 Procedural amendment (voluntary) July 16, 1985 Commissioner of the Japan Patent Office 1. Indication of case 1988 Patent application No. 78131 2. Name of invention Method for forming deposited film 3 , Relationship to the case of the person making the amendment Patent applicant (100) Canon Co., Ltd. Kamasha 4, Agent address: 5-9-20, 1-9, Akasaka, Minato-ku, Tokyo, Claims column of the specification to be amended and a column for detailed description of the invention. 6. Contents of amendment 1) The claims are amended as shown in the attached sheet. 2) Specification @ page 5, lines 7 to 8, page 11 to line 1
Line 2, lines 15 to 16 on the same page, lines 18 to 18 on the same page
line, page 8, line 13 and line 17 of the same page, the statement [in genus ■ or genus V] was changed to [in genus ■ or genus V].
Correct each statement. 3) The description of "genus m" on page 8, line 1 and page 15, line 3 of the specification is corrected to "group Ⅰ". 4) The description of "Group V" in the second line of page 8 of the specification is corrected to the description of "Group V." 5) The statement "belongs to" on page 14, line 14 of the specification is corrected to "belongs to". Claims (1) In the deposition chamber in which the support is placed, the general formula;
A gaseous atmosphere is formed between a chain silane compound having a side chain represented by H2n+2 (n≧4), a halogen compound, and a compound containing an atom belonging to the ml or vol of the periodic table. A method for forming a deposited film, characterized in that a deposited film containing silicon atoms and atoms belonging to ml or vl of the periodic table is formed on the support by excitation and decomposition using light energy. .

Claims (1)

[Claims] (1) In the deposition chamber in which the support is placed, the general formula;
Forming a gaseous atmosphere of a button-type silane compound having a side chain represented by H2n+, (n≧4), a halogen compound, and a compound containing an atom belonging to Group I or Group V of the periodic table, A compound 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. Method of forming deposited film.