JPS63224216A - Formation of deposition film - Google Patents

Abstract

PURPOSE:To contrive both improvement in deposition speed and uniformity of film thickness by a method wherein precursor is passed through activated space without contacting to an active species, it is introduced into film-forming space, and a deposition film is formed by the chemical reaction of the precursor and the active seed introduced into the film-forming space. CONSTITUTION:Glass is used for a substrate 103, the substrate 103 is placed on a supporting stand 102, a film-forming chamber 101 is evacuated and depressed by an exhaust system, and the substrate is heated up by a substrate heating heater 104. At this point, Si2F6 is introduced from a cylinder through a feeding tube 108. At this time, a furnace 109 is heated up to 700 deg.C in advance. The Si2F6 gas passed through the inflared-ray image furnace 109 is decomposed, and the precursor such as SiF2* is grown. The SiF2* is a radical having a long life, it can be passed through a fine precursor carrying tube 110 having the inside diameter of 4 mmphi. This precursor and H* are chemically reacted, and a deposition film is formed on the substrate 103. As a result, a deposition film of high quality having various kinds of film qualities ranging on a large area can be formed uniformly.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography on photovoltaic elements, line sensors for image input, and imaging. The present invention relates to a method suitable for forming deposited films used in devices and the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using the vacuum evaporation method, plasma CVD method, CVT) method, two-reaction forward sputtering method, ion grating method, photo-CVD method, etc. Generally, plasma CVD method is used. It is widely used and has been commercialized.

According to Hyakunen et al., deposited films composed of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity and mass production, including uniformity and reproducibility. There is room to improve overall characteristics.

The reaction process in forming an amorphous silicon deposited film using the conventionally popular plasma CVD method is considerably more complex than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. . In addition, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation formula, etc.). Because of the combination of parameters K, the plasma sometimes becomes unstable, which often has a significant adverse effect on the deposited film.

Furthermore, it is necessary to select a parameter specific to each device for each device, making it difficult to generalize manufacturing conditions.

On the other hand, in order to develop an amorphous silicon film with electrical and optical properties that fully satisfy various uses, it is currently considered best to form the film by plasma CVD.

In the plasma CVD method, Hyakunen et al.
Due to the complicated formation parameters of the R film, it is difficult to create uniform film formation conditions over and over again, especially when forming a deposited film over a large area. We regret that it is difficult to form a film with good reproducibility while fully satisfying the uniformity of film thickness and film quality. In addition, when aiming for mass production, the management items for mass production become complex, the tolerance range for management is narrow, and the adjustment of equipment is delicate, so these are issues that need to be improved in the future. This is pointed out as a point.

On the other hand, the conventional technique using the normal CVD method requires high temperatures and cannot produce a deposited film with practically usable characteristics.

As mentioned above, it is highly desirable to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practical properties and uniformity.
ing.

This applies not only to the amorphous silicon film mentioned above, but also to polycrystalline silicon films (including those exhibiting a microcrystalline phase).
Non-monocrystalline silicon films, single-crystalline silicon films, and other non-single-crystalline or single-crystalline functional films 1, such as silicon
The same can be said of the darmanium alloy film, silicon nitride film, silicon carbide film, and silicon oxide film.

[Problems to be solved by the invention]

The present invention has been made to eliminate the above-mentioned drawbacks of the plasma CVD method and at the same time to provide a new deposited film formation method that does not rely on conventional formation methods.

The present invention also maintains the characteristics of the formed film, improves the deposition rate, and deposits a film with a uniform thickness over a large area or on any desired local area with high efficiency and reproducibility. This was developed to provide a method for forming a deposited film that can be produced using

The present invention has also been made to provide a deposited film forming method that can simplify the management of film forming conditions and easily achieve mass production of films.

[Means for solving problems]

In the deposited film forming method of the present invention, a precursor serving as a raw material for forming a deposited film generated in an activation space ω) is placed in a film forming space (4) for forming a deposited film on a substrate; space(
In the method for forming a deposited film in which a deposited film is formed on the substrate by introducing an active species that is generated at 0 and interacts with the precursor, the active species has a catalytic effect in the activation space C). The precursor is generated by a heating element made of a single transition metal element or an alloy thereof and introduced into the film forming space, and the precursor is allowed to pass through the activation space (Q) without coming into contact with the active species. The precursor and active species thus introduced into the film forming space (4) chemically react to form a deposited film.

According to the present invention, the tth film forming space (4
), in order to generate plasma, a precursor that is a raw material for forming a deposited film that is generated in the activation space Φ) interacts with the precursor that is generated in the activation space (Q). Since a deposited film is formed by introducing active species into the entire film forming space (6) and causing a chemical reaction, the deposited film that is formed is free from etching effects or other adverse effects caused by K, such as abnormal discharge effects, during film formation. You will not receive any.

However, in the present invention, in order to generate active species using a heating element made of a single transition metal element or an alloy having a catalytic effect in the activation space (C), for example, when generating active species by plasma discharge, In comparison, A
It is possible to stably supply active species over a wide pressure range without using a diluent gas that has a discharge-dependent effect such as R, and by arbitrarily selecting the shape of the heating element and the heating temperature. The amount of active species produced can be easily controlled.

In addition, in order to allow the precursor to pass through the decomposition and excitation space (C) where the active species are generated without contacting the active species, and to introduce the precursor into the film forming space (4) together with the active species, the precursor and the Since the flow f'L with the active species can be made uniform and the chemical reaction can be efficiently carried out near the substrate, a deposited film with reproducibility can be formed.

Friend, according to the method of the present invention, the shape of the activation space (Q) for generating active species can be simplified, the energy efficiency for generating active species is high, and equipment and production costs can be reduced. Can be done.

Note that the "precursor" in the present invention refers to a material that can be used as a raw material for a deposited film to be formed. "Active species" are those that chemically interact with the precursor, for example, give energy to the precursor, and chemically react with the precursor to more efficiently deposit the precursor. It refers to something that has the role of bringing things into a state where they can be formed.

Therefore, the active species may include constituent elements constituting the deposited film to be formed, or may not include such constituent elements.

It is desirable to select transition metals that serve as the heating elements used in the present invention to be those that are difficult to mix into the deposited film due to sublimation, scattering, etc. It is necessary to choose suitable activation conditions.

Such materials include those from period 4 or 5 of the periodic table.
Mention may be made of metals and alloys of the elements of the period and the sixth period, and among these, ■, v.

Transition metals belonging to groups (1), (2), and (2) can be suitably used.

Specifically, for example, "e Nd I Cr I Mo
+ W −Fo z Ni, Co, Rh t
Pd, MnsAg*Zn, Cd.

Pd-Ag, Ni-Cr, W-Rex W-
Examples include Mo.

In addition, in the present invention, the heat generation temperature of the heating element made of a transition metal provided in the activation space (C) is preferably 150
°C to 3500 °C, more preferably 250 °C to 2800 °C,
The optimum temperature is 550°C to 2200°C. By selecting the shape of the heating element, such as linear, filament, mesh, flat plate, or honeycomb, the active species can be The generation cross section can be changed.

In the present invention, the precursor is activated in the activation space (inside Q,
It can be generated by thermal energy from the heating element. As such a method.

The raw material gas for forming the deposited film, which is easily decomposed at a relatively low temperature, may be introduced into a gas inlet pipe such as a quartz tube, which is disposed near the heating element in the activation space C).

In the present invention, the raw material gas for forming a deposited film used for film formation is a compound having a main skeleton of silicon and containing halodane and/or hydrogen in its molecule.

Examples include compounds with carbon as the main skeleton and compounds with germanium as the main skeleton. Hydrogen and compounds that generate hydrogen radicals in an excited state include hydrogen fluoride, hydrogen chloride, etc. It will be done.

These compounds may be used alone or in combination if necessary.

As the compound having silicon as the main skeleton, for example, a compound obtained by substituting some or all of the hydrogen atoms of a chain or cyclic silane compound with a halogen atom is used, specifically, for example,
81 Y (u is an integer greater than or equal to 1, u 2u+2 Y is F, CL, Br, and engineering) At least 1 to 11 elements are selected. (Ma is an integer greater than or equal to 3,
Y has the meaning given above. ) Cyclic silicon halide, 31uHxYy (u and Y have the above-mentioned meanings).

x+y=2u or 2u+2. ) and the like can be mentioned.

Specifically, for example, another F4. (SiF2)5. (Si
F2) 6° (SiF2) 4.312F6.813F8.
5l) IF3.5IH2F2゜5t2H2F4.312
H3F3.5IC24, (SIC22)5゜SiBr4
1 (SiBr2)515i2Ct61512Br6
．． 5IHC13eSiHBr3.5IHI3.512C
Examples include those that are in a gas state or can be easily gasified, such as L5F3.

These silicon compounds may be used alone or in combination of two or more.

Further, as a compound having carbon as a bioskeleton, for example, a compound in which some or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound are substituted with halo atoms is used, and specifically,
For example, cuY2u+2 (u is an integer greater than or equal to 1, Y is F
, CL, Br, and at least one element selected from (). ) chain halodanide carbon, C
Cyclic silicon halide represented by vY27 (v is an integer of 3 or more, Y has the above meaning), CuHXY,
(U and Y have the above-mentioned meanings. X+'!=2u or 2u+2).

Specifically, for example, CF4. (CF2)5. (CF
2) 6° (CF2)4. C2F6. C3F8. C
HF3. CH2F2. CCl4゜(CCt'2)5
, CBr4(CBr2)51 C2C1b , C
2Br61CHCL6. CHI, , C2CL, F
, and those that are in a gaseous state or can be easily gasified.

These carbon compounds may be used alone or in combination of two or more.

Further, as the compound having r-rumanium as a main skeleton, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrogenated r-rumanium compound is replaced with a halodane atom is used, and specifically, for example, 1.

GeuY2u+2 (u is an integer greater than or equal to 1, Y is F, c
At least one element selected from Z, Br, and ■. ) Chain germanium halide G
Cyclic halogenated r-rumanium represented by evY2v (v is an integer of 3 or more, Y has the above meaning), G e
uHxYy (u and Y have the above meanings.x+
y=2u or 2u+2. ), and the like.

Specifically, for example, aeFa, (GeF2)5. (G
6F2)61(GeF2)4. Ge2F6. Ge3
F8. GeHF, , GeH2F2゜Ge2H2F
4. Ge2H5F3 r GeC441 (GaCl2
)51GeBr4. (GeBr2)5, Ge2C
66, Ge2Br6, GsHCt5+GeHBr3
．． Examples include those that are in a gaseous state or can be easily gasified, such as GeHI, Ge2CL3F3, etc.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation.

The impurity elements to be used include, as p-type impurities, elements of group A of the periodic table, such as B, At, Ga,
Suitable examples include In, Tt, etc., and examples of i-type impurities include elements 1 of group V A of the periodic table, such as P +
Preferred examples include As, Sb, Bi, and the like, with As, P, and Sb being particularly optimal. The amount of doped impurities is determined to achieve the desired electrical
It is determined as appropriate depending on the optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select Such compounds include PH,, P2H4, PF
3. PF5. PCB, .

A@)t, , AsF3. AsF5. AaCL,
, SbH3, SbF5゜BFs, BC63*
BBr31 B2H6+ B4H1o + BAH?
.

Examples include B5H111B6H101B6H12.

The compounds containing impurity elements may be used singly or in combination of two or more.

A compound containing an impurity element as a component may be introduced into the decomposition space or the divided excitation space directly in a gaseous state or mixed with a raw material gas for film formation.

In the present invention, since an inert gas (He, Ar, etc.) is not used for excitation of the deposited film forming raw material gas, the active species generating raw material gas, and the compound containing impurity elements, these gases are not present in the deposited film. A high quality deposited film can be obtained without any contamination.

Hereinafter, one embodiment of the method of the present invention will be described in detail based on the drawings.

FIG. 1 is a schematic diagram of a deposited film forming apparatus that can be used to carry out the present invention.

In FIG. 1, 101 is a film forming chamber, and a support stand 102
A desired base 103 is placed thereon.

According to the method of the present invention, it is possible to lower the temperature of the substrate 103, so a film of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc. It is possible to use sheets, glass, etc. Of course, metal 1 alloys, silicon, kelmanium, GaAa, or ceramics can also be used.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with power through a conductive wire 105 and generates heat. The heater 104 heat-treats the substrate 103 before film formation, performs annealing treatment after film formation to further improve the properties of the formed film, or heats the substrate 103 during film formation as necessary. Used for heating.

When the substrate is heated in carrying out the method of the present invention, it is desirable that the substrate heating temperature is preferably 30 to 450°C, more preferably 50 to 350°C. 10
6 is a thermocouple for monitoring temperature.

107 is connected to an exhaust system (not shown), and can be evacuated by a target molecular pump, a mechanical booster pump, and a rotary pump (not shown).

Reference numeral 108 denotes a raw material gas supply pipe, through which various raw material gases and, if necessary, a carrier gas are supplied from a supply system (not shown) while being controlled to a desired flow rate by each mass flow controller. The raw material gas is excited in an infrared image furnace 109 to generate a precursor.

That is, the tube inside the furnace 109 is connected to the activation space (B
). The raw material gas containing the precursor is introduced into the film forming space (A) together with the active species through a precursor transport pipe 110 that passes through the activation space (C) for generating active species.

Reference numeral 111 denotes an outer tube, which has a double tube structure together with the precursor transport tube 110.

Reference numeral 112 is a supply pipe for active species generation gas and, if necessary, excitation and/or carrier gas, which are introduced into the outer tube 111 from a supply system (not shown) after being adjusted to desired flow rates by a mass flow controller. I can vomit.

Reference numeral 113 is a heating element made of a simple substance or an alloy of a transition metal element having a catalytic effect, and generates active species by its catalytic action.

114 is a power source for the heating element 113.

115 is a vacuum gauge that indicates the degree of vacuum within the reaction chamber 101.

According to the present invention, for example, the precursor transport tube passes through the activation space (C) in the outer tube 111 where active species are generated without coming into contact with the active species immediately after generation, and the precursor transport tube passes through the film forming space (A) so as not to come into contact with the active species immediately after generation. For the first time, the precursor and active species come into contact and the chemical reaction proceeds.

Thermal energy is used in Figure 1 as the activation energy for the raw material gas, but other sources include discharge energy such as DC and RF microwaves, light energy, or energy beams that can be converted into thermal energy (laser light, X-rays, etc.). , electron beam, single molecule beam, etc.), or the energy of chemical reactions.

The precursors and active species formed by the above method uniformly associate in the film forming space (A) and cause a chemical reaction, resulting in a desired deposited film on the substrate 103 in the film forming space (A). is formed.

〔Example〕

Specific examples of the present invention are shown below.

[Example 1] Using the device shown in Fig. 1, the following operations were carried out to inhale -8l@
was created.

First, Corning 7059 glass was used as the substrate 103 and placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to 10-'Torr. Corning 70 by substrate heating heater 104
59 glass substrate was heated to 250'C.

Therefore, from the gompe (not shown) through the supply pipe 108,
I made 2F6 10 SCCM 4 people. At that time, the temperature of the furnace 109 was preheated to 700°C.

On the other hand, H2 gas is supplied from the gas supply pipe 112 at 15 SCCM.
was introduced into the outer tube 111.

On the other hand, the rotation speed of a mechanical booster puffer (not shown) in the exhaust system 107 was adjusted to maintain the pressure indicated by the Paratron vacuum gauge 114 at 0.25 Torr. Next, a W filament 113 t-1800'CK used as a heating element made of a transition metal element having a catalytic effect was heated to generate H4 as an active species in the outer tube 111.

It should be noted that when attempts were made to generate plasma discharge using a plasma generation furnace using μ waves instead of the W filament under the above-mentioned gas flow rate and pressure conditions, stable discharge was not obtained.

On the other hand, the 81□F6 gas that passed through the infrared image furnace 109, which was preheated to 700°C, was decomposed into n, Si
A precursor such as F2'' is generated.SiF2'' is a long-lived radical and could be passed through the thin precursor transport pipe 110 with an inner diameter of 4 mm. This precursor and H
o caused a chemical reaction and formed a deposited film on the substrate 103.

f'L7'c a-81:H(:F) obtained by the above method
Although the inner diameter of the outer tube 111 is 38 mm, the film thickness distribution is ±10 mm within the range of 70 mm on the base 103.
%, the variation in properties such as dark conductivity (σd), activation energy (El), and optical pad/gap f (Ego, t) was ±5% or less.

[Example 2] Using the apparatus shown in FIG. 1, an Sl (μX-81) film containing a microcrystalline phase, which is a form of *-8i, was formed by the following operations.

In the same manner as in Example 1, Si2F6 was 88 CCM,
The H2 gas flow rate was adjusted to 80 SCCM, and the pressure inside the film forming chamber 101 was adjusted to 0.15 Torr. Film formation was performed by turning on the power source of W filament at 9 watts.

The S1 film obtained by the above method has a Raman spectrum of 465
It was found that the film was an a-81:H(:F) film containing about 80× microcrystalline phase shifted from cm-'.

Also, 81□F6 gas at 8 SCCM, 5IF4 at 1
PF5 gas diluted to 20 SCCM is supplied from the raw material gas supply pipe 108, while H2 gas is supplied at 130 SCCM.
M was supplied to the outer tube 111 from the gas supply tube 112. Next, the pressure inside the film forming chamber 101 was adjusted to 0.15 Torr. Turn on the W filament power of 160W and nf
An a-sx:n (:F) film of i was formed. This n type a-
The 81:H (:F) film contained a microcrystalline phase of 80 to 120X as a result of Raman spectrum and transmission electron microscopy (TEM) observation. The characteristics of the deposited film are σ, = 1.8 CS
, 10n'), Ea=0.07eV, E 1.8
・V, and each variation was within ±4% within the range of opt 60■φ.

In addition, 512F6 is 78CCM%81F4 and 1%
BF diluted to 20 SCCM to raw gas supply pipe 1
H2 gas was supplied from the gas supply pipe to the outer pipe 111 at 150 SCCM. Next, the pressure in the film forming chamber 101 was adjusted to 0.15 Torr K m, and the power source power of the W filament was applied to 160 W to form the p-type a-31:
A H(:F) film was formed. This p-type a-6i :H(
:F) The film contains a microcrystalline phase, and the characteristics of the deposited film are C
6=1.1. C8/crn), E = 0.06 eV
,E. The uniformity was also good, with variation within ±4% within the range of pt=2.1 eV and 50 mφ.

[Example 3] Using the apparatus shown in FIG. 1, a polycrystalline silicon (polySt 2 ) film was formed by the following operations.

In the same manner as in Example 1, S1 □ F6
.

The H2 gas flow rate was 18080 CM, and the pressure inside the film forming chamber 101 was adjusted to 0.05 Torr.

Next, the power supply power of the W filament was increased to 200 W to form a silicon film.

Si film IITEM observation results obtained by the above method 605
Poly 81 had a duraine size of 3800X or more within the range of wφ.

Furthermore, using a silicon wafer as the substrate 103, epitaxial growth was attempted at a substrate temperature as low as 250.degree.

After a film was formed under the above film forming conditions using a silicon wafer whose surface parallel to the substrate support was oriented in the (111) plane, epitaxial growth was confirmed from the reflection electron diffraction rLHEED (1) pattern.

[Example 4] Using the apparatus shown in FIG.
:Ge film was formed.

81 F Gas flow rate is 58 CCM, G・2F6 is set to Q, 5 SCCM is set, and raw material gas supply pipe 10 is set at the same time.
On the other hand, H2 gas was supplied from the gas supply pipe 112 to the outer tube 111 at 30 SCCM. Next, the pressure in the film-forming chamber was adjusted to 0.2 Torr K, and a 110 W power supply for the W filament was applied to form a film.

The *-8l:Go:H(:F) film obtained by the above method had a "gopt" of 1.38 eV (±2
%) and a narrow optical bandgap width was obtained.

[Example 5] Using the apparatus shown in FIG. 1, the solar cell shown in (at, (bl) in FIG. 2 was produced by the following operations.

The base 203 is made of 5US-304 and has a reflective metal film 20 on top.
4, Ag was evaporated at 2500X.

First, the SUS substrate on which Ag was vapor-deposited was placed on the apparatus shown in FIG. 1, and the n-type μX-5t film 2 was
a-81:H(:F
) @ 206 was stacked at 6000X, and p-type μX-5t film 207 was stacked at 150X under the conditions of Example 20. Next I
TO film 208 was deposited in an approximately 900X oxygen atmosphere. Next, apply conductive paste 209 at intervals of 5sl11 and
．． Nine solar cell submodgieres of 4w x 25.4ms square were fabricated. Let this element be (&).

In addition, a tandem structure solar cell (bl) shown in FIG. 2(b) was fabricated in the same manner as the above method.
Figure 2 in Figure 1 (the same elements as at are represented by the same symbols and were produced using the same formation method. 210 a-81: Ge
The :H (:F) layer was deposited in 25001 layers under the conditions of Example 4. Also, the a-81:H (:F) layer 206 has a density of 3500
It was set to 1.

Table 1 shows the evaluation results of the solar cell (al e (b)).The average value of photoelectric conversion efficiency is 25.41111X2
The average value of nine 5.4W square Salamosieres was found to be within ±6.3% for both elements (a) and (bl) formed according to this example.

[Example 6] Fig. 3 shows an apparatus in which the activation energy in the raw material gas activation space (B) in the apparatus shown in Fig. 1 was changed from thermal energy of an infrared image furnace to discharge energy by a microwave oscillator. Ta.

The same elements as in FIG. 1 are represented by the same symbols. 311 is a plasma generation furnace, 312 is a microwave waveguide, 313 is a microwave generator, and the pressure in the activation space (B) is a precursor transport pipe. By reducing the inner diameter of the film 110, the pressure inside the film forming space 101 can be kept high, making it possible to stabilize the plasma discharge.

Using the apparatus shown in FIG. 3, a Shiro-8i film was prepared by the following operations.

5IF4 is supplied from a cylinder (not shown) through the supply pipe 108.
0800M was introduced and microwave power of 200W was input. Thereafter, a deposited film was formed using the same procedures and operations as in Example 1.

The a-8l:H(F) film formed by the above method is the substrate 103.
Within the range of 60 m + φ, the film thickness distribution is less than ±7%, and the variation in characteristics such as dark conductivity (σd), ημτ, activation energy (Ea), optical breadth gap f (Ego, ) is less than ±4 factor. Ta.

[Example 7] St (μX-
5t) A film was formed. SiF4 in the same manner as in Example 6
Introducing 60800M gas and increasing the microwave power to 220M
I put in a W. The deposited film formed by the same procedure and operation as in Example 2 has a Raman spectrum shifted from 465crn and contains a-8i:H microcrystals of about 60X.
(:F) It turned out to be a film.

In addition, in Example 2, the n-type a-8 film was formed by changing the 512F6 gas to 5IF4 gas and setting the flow rate to 20 SCCM.
i:H(:F) film has Raman spectrum, T111M
As a result of observation, it contained a 70-110X microcrystalline phase. The characteristics of the deposited film are σdm1.6 Ca/an], Ea mO
, o 6 eV, E,. pt# was 18 mV, and each variation was within ±5 yen within a range of 60 mφ.

Furthermore, in Example 2, 512F6 gas was replaced with SIF4 gas and the flow rate was set to 10 SCCM to form a film. The p-type a-81:H(:F) film obtained in this way contains a microcrystalline phase, and the characteristics of the deposited film are (F d -1,0(a/
z), Eaxo, 06eV.

Ego, ri2. OeV, and the uniformity was good with variation within ±5 inches within the range of 50 cod φ.

[Example 8] A polycrystalline silicon (poly-St) film was formed by the following operations using the apparatus shown in FIG.

A film was formed in the same manner as in Example 3, replacing 512F6 gas with SiF4 gas and changing the flow rate to 15 SCCM.

As a result of TEM observation, the obtained silicon film was found to be poly-8i with a diameter of 3200X or more within a range of 50 mφ.

Furthermore, when a silicon wafer is used as the base 103,
Epitaxial growth was attempted at a low substrate temperature of 250°C. After forming a film under the above conditions using a silicon wafer whose surface parallel to the substrate support has a (111) plane orientation, it was confirmed from the RHEED pattern that it was epitaxial growth.

[Example 9] An a-8l:Ge:H (:F) film was formed using the apparatus shown in FIG. 3 and following the same procedure and operation as in Example 4.

In Example 4, Si2F6. The film was formed by changing the /l/s to SiF4 and setting the flow rate to 10 SCCM.

The resulting a-8t:Go:H(:F) film had a narrow optical bandgap width of 1.39 eV (±3%) within the range of 60 mφ.

[Example 10] Using the apparatus shown in FIG. 3, the solar cell shown in FIGS. 2(a) and 2(b) was produced by the same procedure and operation as in Example 5.

In Example 5, the n-type μx-s+ film was formed under the conditions of Example 7, the a-8t:H(:F) film was formed under the conditions of Example 60, and the p-type μX The -5t film was formed under the conditions of Example 7, and the resulting device is designated as (a').

Further, a solar cell (b') having a tandem structure as shown in FIG. 2(b) was produced in the same manner as the above method. 210 a-
The 81:Ge:H(:F) layer was deposited under the conditions of Example 9.

Table 1 shows the evaluation of the above solar cells (a + (b). The average value of photoelectric conversion efficiency is 25.4 mX 25.4
The average value of nine submodules of m+ angle is the variation of ±7.
It was recognized that the temperature was less than 0.

〔Effect of the invention〕

As confirmed from the above examples, according to the deposited film forming method of the present invention, it is easy to uniformly form deposited films having various film qualities with high quality over a large area. A deposited film can be formed with good reproducibility and high efficiency.

Further, a polysilicon deposited film can be obtained at a low substrate temperature of 250° C., and furthermore, it is possible to simplify the management of the deposited film forming apparatus and conditions and to easily mass-produce the film.

[Brief explanation of drawings]

FIGS. 1 and 3 are schematic diagrams of deposited film forming apparatuses that can be used to carry out the present invention, respectively. FIGS. 2(a) and 2(b) are schematic diagrams each showing the structure of a solar cell that can be produced by the method of the present invention. 101...Reaction chamber, 102...Substrate support, 103
...Base, 104...Heater for heating the base, 105
... Conductor wire, 106 ... Thermocouple, 107 ... Exhaust system, 108 ... Raw material gas introduction pipe, 109 ... Infrared image furnace, 110 ... Precursor transport pipe, 111 ... Outside Pipe, 112... Gas supply pipe, 113... W filament, 115... Vacuum gauge, 311... Activation energy introduction tube, 312... Microwave oscillator, 313...
...Microwave waveguide, 203...SUS base, 20
4... Reflective metal film layer, 205-1, 205-2...
・N-type-μX-3t layer, 206-...a-8l:H(:
F) layer, 207-1, 207-2...p type-μx-s
i layer, 208...ITO layer, 2,09...conductive paste, 210...a-8i:Ge:H(:F).

Claims (1)

[Claims] In a film forming space (A) for forming a deposited film on a substrate, a precursor that is a raw material for forming a deposited film is produced in an activation space (B), and a precursor is produced in an activation space (C),
In the deposited film forming method of forming a deposited film on the substrate by introducing an active species that interacts with the precursor, the active species is a transition metal element having a catalytic effect in the activation space (C). The precursor is generated by a heating element made of a single substance or an alloy of and introduced into the film forming space (A), and the precursor is
The precursors and active species introduced into the film forming space (A) are passed through the activation space (C) without coming into contact with the active species and are introduced into the film forming space (A). A deposited film forming method characterized in that a deposited film is formed by reaction.