JPS62150709A - Functional deposition film and manufacture thereof - Google Patents

Abstract

PURPOSE:To enable achievement of the simple control of film-forming conditions and the mass production of a film contriving to improve deposition speed by previously using activated active species in the space different from a film- forming space. CONSTITUTION:An Al2O3 substrate 207 is previously inserted in a film-forming chamber (A) 201 and F2 gas 220 SCCM is introduced via a gas introducing pipe 212 in an activating chamber (B) 202 as a raw material gas for making an activated halogen. Additionally, (C2H5)2Zn is introduced in the activating chamber (B) 202 as a raw material gas for forming a semiconductor via a gas introducing pipe 211. Then, the pressure in the film-forming chamber (A) 201 is made 0.002torr and discharge energy is applied to the activating chamber (B) 202. This state is kept for 1.5hr and a ZnS film approx. 2.2mum thick is deposited on the Al2O3 substrate 207 in the film-forming chamber (A) 201.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to monofunctional films, particularly amorphous to polycrystalline so-called non-monocrystalline functional deposited films useful for applications such as semiconductor devices. and its manufacturing method.

<Prior art> Vacuum deposition method, plasma CVD method, thermal CVD method, photo CVD method 1 reactive sputtering method, ion blating method, etc. have been tried for forming the deposited film, and generally, plasma CVD method is used. Laws are widely used and corporatized.

Hyakunen et al., Deposition I obtained by these deposited film formation methods
II is required to be applied to electronic devices that require more advanced functions, so it has improved electrical and optical characteristics,
Fatigue characteristics due to repeated use, usage environment characteristics, and uniformity.

There is room for further improvement in overall characteristics in terms of productivity and mass production, including reproducibility.

By the way, the reaction process in forming a deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional so-called thermal CVD method, and there are many unknown points about the reaction mechanism. There wasn't. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, structure of the Tr1 pole structure 9 reaction vessel, pumping speed, plasma generation 1L-4--
1tJ, ++71-F-II-/F%4-) LTS+J
-+J-λ4rr)m combination, the plasma sometimes becomes unstable and often has a significant adverse effect on the deposited film formed. Furthermore, the actual situation is that parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions.

Among these, the plasma CVD method is currently considered to be the best method to form an amorphous silicon film, since it can produce electrical and optical properties that fully satisfy various uses. .

According to Hyakunen et al., depending on the application of the deposited film, it is important to increase the area, uniformity of the film thickness, etc. II! Since it is necessary to fully satisfy J quality uniformity and achieve reproducible mass production, the formation of deposited films by the plasma CVD method requires a large amount of capital investment for mass production equipment, and the mass production is difficult. The management items for this have become more complex, the allowable range of management has become narrower, and the adjustment of equipment has become more delicate, and these have been pointed out as the dark side of post-4 improvement surgery.

Furthermore, depending on the type of deposited film, the plasma CVD method is not necessarily suitable, and in addition, the effect of plasma damage on the film, which is a drawback of the plasma CVD method, may affect the required film properties and prevent it from fulfilling the desired function. Examples include becoming. Particularly in the production of deposited films for highly functional electronic devices, the effects of plasma damage mentioned above directly appear on the film properties and must be avoided as much as possible.

On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with characteristics that are necessarily satisfactory at a commercial level.

These problems to be solved are particularly related to periodic table I
This is a concern when creating a functional deposited film composed of Group I to Group II elements.

As mentioned above, in forming a monofunctional film, there is a strong desire to develop a forming method that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity.

Purpose of the Invention The present invention aims to eliminate the drawbacks of the above-mentioned conventional deposited film forming methods, particularly the plasma CVD method, and at the same time provide a novel deposited film forming method that does not rely on conventional forming methods.

The purpose of the present invention is to easily control the functional characteristics, maintain at least the characteristics of the high-quality film obtained by conventional methods, and improve the deposition rate while simplifying the management of film formation conditions. It is an object of the present invention to provide a deposited film and a method for forming the same, which can easily achieve mass production of the film.

Structure> The functional deposited film of the present invention comprises a compound (A) and a compound (B) represented by the following general formulas (A) and (B), respectively, which are raw materials for forming a functional deposited film, and Compounds such as (A
) and the compound (B), when introducing the activated halogen into the film forming space, the pre-oil distributing halogen is introduced into the transport space (
A), the compound (A) and the compound (B) are introduced into the film forming space through a transport space (B) which is provided in the transport space (A) and communicates with the film forming space. It is characterized by being formed by a chemical reaction.

The method for producing a functional deposited film of the present invention uses the following general formulas (A) and (
Compound (A) and compound (B) respectively represented by B),
An activated halogen that chemically reacts with at least one of these compounds (A) and (B) is introduced into a film forming space to form a functional deposited film on a substrate disposed within the film forming space. In the method for producing a functional deposited film, the activated halogen is transported into a transport space (
Through A), the compound (A) and compound (B) are
Each film is introduced into the film forming space through a transport space (B) provided in the transport space (A) and communicating with the film forming space.

A a B b -----------1----(B
) However, 2m is a positive integer equal to or an integral multiple of the valence of H, n is a positive integer equal to or an integral multiple of the valence of M, M is an element belonging to Group II of the periodic table, and R is hydrogen. (H), halogen (X), and a hydrocarbon group, respectively.

a is a positive integer equal to or an integral multiple of the valence of B, n is A
A positive integer equal to or an integral multiple of the valence of
), each represents a hydrocarbon group.

<Specific description of the invention> In the present invention, the activated halogen is contained in one feeding space (A).
Also, compound (A) and compound.

The compound (B) is introduced into the film forming space through the transport space (B), but by changing the opening position of the transport space (B) in the transport space (A) variously, the compound (A) and The residence time of the compound (B) in the transportation space (A) must be set appropriately.
Nail muru metrou (h) no lh
The transport speed of the plant (B) in the transport space (B) can also be selected as one of the management parameters for controlling the residence time.

In the present invention, the transportation space (A) and the transportation space (B
) is open to the film forming space, where activated halogen or
When at least one of the compound (A) and the compound (B) is excited as necessary, the method is appropriately determined depending on the lifetime of the compound (A) in the excited state or the compound (B) in the excited state.

In the case of the present invention, the compounds (A) and (B) are generally transported to the film forming space in their ground state, while the activated halogens used are often of relatively short lifespans, so the transport The opening position of the space (A) to the film-forming space is preferably close to the film-forming space.

The opening of the transport space (A) to the film forming space and the transport space (
It is desirable that the opening of B) into the transport space (A) is shaped like a nozzle or an orifice. In particular, in the case of a nozzle-shaped nozzle, by positioning it near the film-forming surface of the substrate disposed within the film-forming space of the nozzle opening, the film-forming efficiency and the effective raw material consumption efficiency can be significantly increased.

In the present invention, the activated halogen is generated in the activation space that communicates with the transport space (A) upstream thereof, and the activated halogen is
) and the compound (B) are excited in an excitation space that communicates with the transport space (B) upstream, if necessary, but the present invention is not limited to this. For example, the transport space (A) can also serve as an activation space, and transport space (B) can also serve as an excitation space.

In particular, when both transport spaces are used as activation space and excitation space, respectively, the same means can be used as activation means and excitation means without providing them separately.

For example, by making the transport space (A) and the transport space (B) have a double glass tube structure, and providing an RF plasma device or a microwave plasma device around the outer glass tube, the transport space (A) and the transport space (B) can be placed at the same position in the transport direction. Activated halogen and excited state compounds (A) and (B) can be produced simultaneously.

In the present invention, a transportation space (A) and a transportation space (B),
Preferably, the open opening portion is located inside the film forming space.

The transport space (B) is used for the compound (A) and compound (B) to be used.
) Depending on the type of compound (A) and compound (B), the compound (A) and compound (B) may be separated and transported independently.

In the present invention, a transportation space (A);
By providing not only one double space structure but a plurality of double space structures in the film forming apparatus, the activated halogen introduced into each double space structure,
By changing the types of compound (A) and compound (B),
Furthermore, according to the method of the present invention, deposited films having different characteristics are formed on each -H of the substrate disposed in the film-forming space.
Unlike the D method, the deposition space, activation space, and excitation space provided as necessary are separated, so contaminants from the inner walls of the deposition space and residual gas remaining in the deposition space are prevented. It has the characteristic of being able to virtually eliminate the effects.

In addition, the "activated halogen" in the present invention refers to the above-mentioned compound (
A) and at least one of compound (B), for example, to give energy to compound (A) or compound (B), or with at least one of compound (A) and compound (B). By chemically reacting, the compound (A
) or compound (B) to a state capable of forming a deposited film.

Therefore, the activated halogen may include constituent elements constituting the deposited film to be formed.
Alternatively, it may not include such components.

The above general formulas (A) and (B) used in the present invention
Compounds (A) and (B) represented by each of these chemical reactions occur by molecular collision with the activated halogen in the space where the substrate on which the film is to be formed exists, and form a chemical reaction on the substrate. It is more desirable to select one that spontaneously generates chemical species that contribute to the formation of the deposited film formed in
In the normal state of existence, the activated halogen is inert or has no significant activity, and if the activated halogen is
The compounds (A) and (B) are prepared by applying excitation energy strong enough to not completely dissociate "M" and "A" in the general formulas (A) and (B) before or during film formation. It is necessary to bring the compound into an excited state where it can chemically react with the activated halogen, and one of the compounds (A) and (B) used in the method of the present invention is a compound that can be brought into such an excited state. It will be adopted as

In addition, in the present invention, the compound (A) or the compound (
B) in the above-mentioned excited state will hereinafter be referred to as "excited species (A) or excited species (B)."

In the present invention, the compound (A) or the compound (B) is excited in advance as necessary to form the compound (A) or the compound (B) in an excited state.
In the case of producing B), the excited state compound (A) and the compound (B) from the transport space (B) introduced into the film forming space are
), but preferably has a long life of 0.01 seconds or more, more preferably 0.1 seconds or more, and optimally 1 second or more, but in any case, it is selected and used according to desire. The constituent elements of compound (A) and compound (B) respectively constitute the main components of the deposited film formed in the film forming space.

When forming a deposited film in the film-forming space, the activated halogen is simultaneously introduced into the film-forming space from the transport space (B), and the activated halogen is introduced into the film-forming space from the transport space (B) to form a deposited film.
A) and at least one of compound (B). As a result, a desired deposited film can be easily formed on a desired substrate. According to the method of the present invention, the deposited film that is formed without generating plasma in the growth space is not adversely affected by etching or other effects such as abnormal discharge effects. Further, according to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in an "activation space (C)" different from the film forming space are used. This makes it possible to dramatically increase the deposition rate compared to conventional CVD methods, and at the same time to obtain a high-quality film.In addition, the substrate temperature during deposition film formation can be further reduced. This makes it possible to provide deposited films with stable film quality in large quantities industrially and at low cost.

In the present invention, the activated halogen generated in the activation space (A) is not only generated by the Toichi halogen 1st W lightning, the halogen halogen, or by a combination thereof, but also by the combination of the two. It may be produced by contact or addition.

In the present invention, the following compounds can be mentioned as compounds that can be effectively used as the compound (A) RnMm and the compound (B) AaBb represented by the general formulas (A) and (B).

That is, "M" represents an element belonging to Group II of the periodic table, specifically an element belonging to Group II B of Zn, Cd, and Hg, and "A" represents an element belonging to Group II of the periodic table, specifically. Specifically, O, S, Se.

Compounds having an element belonging to Group ⅠB of Te can be mentioned as compounds (A) and (B), respectively.

rRJ and "B" are monovalent, divalent and trivalent hydrocarbon groups derived from linear and side chain saturated hydrocarbons and unsaturated hydrocarbons, or saturated or unsaturated monovalent hydrocarbon groups. Mention may be made of monovalent, divalent and trivalent hydrocarbon radicals derived from cyclic and polycyclic hydrocarbons.

Unsaturated hydrocarbon groups include not only a single type of carbon-carbon bond but also those having at least two types of bonds among - double bonds, double bonds, and triple bonds. If it is different from achieving the purpose of the invention, it can be effectively adopted.

Further, in the case of an unsaturated hydrocarbon group having a plurality of double bonds, it does not matter whether the double bonds are non-integrated double bonds or integrated double bonds.

Examples of acyclic hydrocarbon groups include alkyl groups, alkenyl groups,
Alkynyl group, alkylidene group.

Preferable examples include alkenylidene groups, alkynylidene groups, alkylidine groups, alkenylidine groups, and alkynylidine groups. In particular, the number of carbon atoms is preferably 1 to 10 degrees, more preferably 1 to 7 carbon atoms, and most preferably carbon atoms. Numbers 1 to 5 are desirable.

In the present invention, the compounds (A) and (B) to be effectively used are selected from those that are gaseous under standard conditions or that can be easily vaporized under the usage environment. "R" and "M" and "A" and r13j listed above
in selecting rRJ and rM as appropriate and desired.
A selection of combinations of J and rAJ and rBJ is made.

In the present invention, specific compounds effectively used as compound (A) include ZnMe3゜CdMe3, Z
nEt3. CdEt3, etc. as compound (B),
Specific examples that can be effectively used include Me2O, M
e2S, Me2Se, Me2Te, Et20. E
t2S.

Et2Se, Et2Te, X20. SX2゜SX4,
SX6, S eX2, S eX4.

5eX6. TeX6H20, H2S, H2Se,.

Examples include H2Te.

In the above, X is halogen (F, C1.

Br, I), Me represent a methyl group, and Et represents an ethyl group.

The lifetime of the activated halogen used in the present invention is
A shorter length is better in consideration of reactivity with A) or/and (B), and a longer length is better in consideration of ease of handling during film formation, transportation to the film formation space, etc. Furthermore, the lifetime of the active species also depends on the internal pressure of the film forming space.

Therefore, the activated halogen used is selected and determined in such a way that a functional film having the desired properties can be effectively obtained, taking production efficiency into account as well, in relation to other film forming conditions. An activated halogen having a suitable lifetime is appropriately selected and used.

The activated halogen used in the present invention has a lifespan appropriately selected in consideration of the above points.
The activated halogen is selected as desired from within the compatible range of chemical affinity with the specifically used compound (A) and/or (B), but preferably its lifespan is Under the circumstances of the scope of the invention, I
It is desired that the time is 0-4 seconds or more, more preferably I x 10-3 seconds, and optimally I x 10-2 seconds or more.
l, yes.

The activated halogen used in the present invention is a compound (
When a chemical reaction with A) and compound (B) occurs in a chain reaction, it is sufficient to minimize its function as an initiator, so the introduction spray introduced into the film forming space is as follows: It is sufficient to secure an amount sufficient to efficiently cause a chain reaction of chemical reactions.

The activated halogen used in the present invention is used in the film forming space (
Before forming the deposited film in step A), the compound (A) and compound (B) or/and the compound (A) and/or the compound (B) are introduced into the film forming space (A) at the same time and contain constituent elements that will be the main constituents of the deposited film to be formed. Chemically interacts with the excited species (A) of the compound (A) or the excited species (B) of the compound (B). As a result, a [-V group compound deposited film having desired functionality can be easily formed on a desired substrate.

According to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature and substrate temperature of the film forming space (A) as desired.

In the present invention, the raw material introduced into the activation space (C) to generate activated halogen is preferably a gaseous or easily vaporizable substance that generates halogen radicals. Done, specifically F2, 0 sentence 2. Br2゜■2 halogen gas, BrF, C pattern F, C
See F3. ClF3. BrF5. BrF7. IF5゜rc
Examples include interhalogen compounds such as fL and IBr, and in addition to these, rare gases such as He and Ar can also be used.

Activated halogen is generated by adding activation energy such as heat, light, or electric discharge to the above-described material in an activation space (C). This activated halogen is transferred to the film forming space (A
).

At this time, the life of the activated halogen is preferably l x l
O-4 seconds or more is required, and having such a lifetime promotes an increase in deposition efficiency and deposition rate, and allows the compound (A) and compound (B) to be introduced into the film forming space (A).
) increases the efficiency of chemical reactions with

Specifically, the activation energy that causes an activation effect on the activated halogen generating substance in the activation space (C) includes thermal energy such as resistance heating, infrared heating, laser light, mercury lamp light, and halogen lab light. light energy, etc.
Examples include electric energy using discharge such as microwave, RF, low frequency, and DC, and these activation energies are applied alone to the activated halogen generating substance in the active space (c). Alternatively, two or more types may be used in combination. The compound (A), the compound (B), and the activated halogen introduced into the film forming space (A) cause a chemical reaction by mutual collision at the molecular level, and deposit a functional film on the desired substrate. However, depending on how each of the compound (A), compound (B) and activated halogen is selected, the chemical reactivity described above may be poor. , or if a chemical reaction is to be carried out more effectively to efficiently produce a deposited film on the substrate,
In the film forming space (A), compound (A) and compound (B)
Or/and reaction promoting energy acting on the activated halogen, such as the activation energy used in the activation space (C) described above, may be used.

Or, before introducing the compound (A) or the compound (B) into the film forming space (A), the compound (A) or the compound (B) is added to the other activation space (D).
Excitation energy may be applied to bring A) or compound (B) into the above-mentioned excited state.

Compound (A) introduced into the film forming space (A) in the present invention
The ratio between the total amount of compound (B) and the amount of activated halogen introduced from the activation space (C) is determined depending on the deposition conditions, compound (
A) and the type of activated halogen, desired characteristics of functional film formation, etc. may be determined as desired, but preferably 1.
000:1 to 1:10 (introduction flow rate ratio) is appropriate, and more preferably 500:1 to 1:5.

When the activated halogen does not cause a chain chemical reaction with the compound (A) or the compound (B), the ratio of the amount introduced is preferably 10:1 to 1:10. More preferably, the ratio is 4:1 to 2:3.

The internal pressure of the film-forming space (A) during film-forming is as follows:
A), the compound (B) and the activated halogen are appropriately determined according to the selected types, deposition conditions, etc., but preferably I 103Pa, optimally lXl0-1
It is desirable that the pressure is 5×102 Pa. In addition, if it is necessary to heat the substrate during film formation, the substrate temperature is preferably 50 to 1000°C, more preferably 100°C.
It is desirable that the temperature is ~900°C, optimally 100~7.50°C.

In the present invention, the substrate used for film formation is:
It may be electrically conductive or electrically insulating. As the conductive substrate, for example, NiCr.

Stainless steel, Au, Cr, Mo, Au, Ir.

N b , T a , V , T i , P L
, Pd, or alloys thereof.

As the electrically insulating substrate, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, seven-rose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. Preferably, at least one surface of these electrically insulating substrates is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, its surface is NiCr.

AM, Cr, Mo, Au, Ir, Nb, Ta.

V, Ti, Pt, Pd, In2O3, 5n02゜ITO
(I n203 + 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, Au, Ag, Pd,
Zn, Ni.

Au, Cr, Mo, Ir, Nb, Ta, V.

The surface is treated with a metal such as Ti or PL'J by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the base body may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined as desired.

In addition to these, semiconductor substrates such as S L , Ge, GaAs, SO3, etc., or the above-mentioned substrates on which other functional films are already formed can also be used.

The method of introduction when introducing the compound (A), the compound (B), and the activated halogen into the film forming space (A) is as follows.
) may be introduced through a transport pipe connected to
Alternatively, the transport pipe may be installed in the film forming space (A) and extended to near the film forming surface of the substrate, and the tip may be introduced with a nozzle shape, or the transport pipe may be doubled. One is transported in the inner tube and the other in the outer tube, for example, the activated halogen is transported in the inner tube, and the compound (A) and the compound (B) are transported in the outer tube, respectively, into the film forming space (A). May be introduced.

In addition, two wooden nozzles connected to the transport pipe are prepared, and the tips of the two wooden nozzles are placed near the surface of the substrate already installed in the film forming space (A). In this process, compound (A) and compound (B) are discharged from the respective nozzles.
) and activated halogen may be introduced in a mixed manner. In this case, it is possible to selectively form a functional film on the substrate, which is convenient because patterning can be performed simultaneously with film formation.

In the present invention, the transport space (B) into the transport space (A)
The position of the opening of the transport space (A) to the film forming space is preferably 0.1 mm to 200 mm, more preferably 1 mm to 100 mm.

Next, the present invention will be explained by citing typical examples of semiconductor members formed by the deposited film manufacturing method of the present invention.

FIG. 1 is a diagram for explaining an example of the configuration of a typical semiconductor member obtained by the present invention.

A semiconductor member 100 shown in FIG. 1 has a layered structure consisting of a semiconductor layer 102 and a gap type electrode 103 on a support 101 for a semiconductor member. In the following description, a case will be described in which the semiconductor layer 102 is formed by the method of the present invention.

The support 101 needs to be electrically insulating. The semiconductor layer 102 is made of, for example, silicon atoms as a matrix, contains halogen (X), and has optionally It consists of amorphous silicon A-SEX(H) containing hydrogen atoms (H).

It will be done.

To form the semiconductor layer 102, first, F is placed in the activation space (A).
A raw material gas for generating activated halogen such as No. 2 is introduced, activated halogen is generated by the action of predetermined activation energy, and is introduced into the film forming space via the transport space (A).

On the other hand, for example, (C2H5)2, Zn.

Compound (A) and compound (B), which are raw materials for semiconductor materials such as H2Se, are mixed with the activated halogen through the transport space (B) on the downstream side of the open opening position to cause chemical interaction. .

A mixed gas consisting of the compound (A), the compound (B), and activated halogen is introduced into the film forming space, and the semiconductor layer 102 is formed on the substrate that has been placed in the film forming space in advance.

Example 1 Using the apparatus shown in FIG. 2, a semiconductor layer was formed on a flat substrate by the following operations, and then a pair of electrodes were formed on the semiconductor layer.

In FIG. 2, 201 is a film forming chamber (A), 202 is an activation chamber (B), 203 and 204 are walls for introducing activation energy and releasing raw material gas for activated halogen, and 205 is a wall for forming a deposited film. 206 is a microwave power source which is an activation energy source, 207 is a glass substrate for forming a deposited film, 208 is a heater for heating the glass substrate, 209 is for a heater electric wire, 2
10 is a substrate holder, 2II is a gas introduction pipe for compound (A) and compound (B), 212 is a pipe for introduction of raw material gas that becomes activated halogen, and 213 is a film forming from the activation chamber (B) 202. This is a nozzle for introducing a mixed gas of activated halogen and compound (A) and compound (B) into chamber (A) 201.

In this embodiment, the tip of the raw material gas introduction pipe 205 was set at a distance of about 5 cm from the nozzle 213.

The A pattern 203 substrate 207 is placed in advance in the film forming chamber (A) 201, and the exhaust valve (not shown) is opened.

The film forming chamber (A) and activation chamber (B) are heated to approximately 1O-5 torr.
The vacuum level was set to . Next, A12 is heated by the heating heater 208.
0-order activation chamber (with o3 substrate temperature maintained at approximately 230°C)
B) F as a raw material gas for activated halogen generation in 202
220 SCCM of two gases were introduced through the gas introduction pipe 212.

Separately, (C2H5)2Z was bubbled with He gas as a raw material gas for semiconductor formation in the activation chamber (B) 202.
n was introduced at a rate of 10 mJl/min, respectively. After the flow rate is stabilized, adjust the exhaust valve to open the deposition chamber (A
) The internal pressure was 0.002Toor. After the internal pressure becomes constant, the microwave power supply 206 is operated and the activation chamber (
B) 280W of discharge energy was applied to 202.

Af in the film forming chamber (A) 201 was kept in this state for 1.5 hours.
A ZnS film of approximately 2.21 Lm was deposited on the L2o3 substrate 207. A comb-shaped/II electrode with a gap length of 2.5 cm and a gap interval of 0.2 mm was formed on the Z n S film thus prepared by ordinary patterning. When a voltage was applied between the electrodes of the sample prepared in this way, the ratio of current flowing 3.2 was still 2×10 , and this value did not change even after 72 hours of continuous light irradiation.

Example 2 In Example 1, compound (A) and compound (
B) respectively, and the amount introduced was 1mmofL/
The thin film shown in Table 1 was formed when the film was formed in substantially the same manner as in Example 1 except that the conditions were as shown in Table 1.

When these thin films were evaluated for electrical and optical film characteristics, it was confirmed that they were all films with uniform thickness, high quality, and excellent film characteristics.

Table 1 Example 3 In Example 1, an RF discharge device (not shown) installed around the nozzle 2173 was used to generate 3.
Power of W was applied to form a plasma atmosphere inside the nozzle 213. In this case, the base 207 was placed at a position 1 cm downstream of the plasma atmosphere so as not to directly touch the plasma atmosphere. A ZnS film with a thickness of approximately 2.4 p.m was formed in one hour after the start of film formation. The substrate temperature at this time is 200″
I kept it at C. Except for the above, the same procedure as in Example 1 was carried out.

When the sample provided with this ZnS film was evaluated in the same manner as in Example 1, it was confirmed that it exhibited good device characteristics.

Furthermore, the ZnS film did not peel off from the substrate and was mechanically excellent.

Example 4 A ZnS film was produced in the same manner as in Example 1 except that Cl gas was used instead of F2 gas in Example 1. It was confirmed that the film properties of this Z n S II@ were also good.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired Trf, gas, optical, photoconductive, and mechanical properties of the formed film are improved, and the reproducibility in film formation is improved. , it is possible to improve the film quality and make the film quality uniform, and it is also advantageous for increasing the area of the film, and it is possible to easily achieve improvement in film productivity and mass production.

Further, since it is possible to form a film at a low temperature, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a layered structure for explaining one embodiment of a semiconductor member produced using the method of the present invention. FIG. 2 is a schematic explanatory diagram showing an example of an apparatus for implementing the manufacturing method of the present invention. 201---1 film formation chamber (A), 202-1---activation chamber (B), 203.204---1 activation energy introduction wall and active species source gas discharge wall, 205---- Gas release pipe, 206--Microwave power source, 207--Glass substrate, 208---Heating heater, 209--Heater electric wire, 210---Substrate holder, 2II-- --Gas introduction pipe, 212---Gas introduction pipe, 213---Nozzle.

Claims (7)

[Claims] (1) Compound (A) and compound (B) represented by the following general formulas (A) and (B), respectively, which serve as raw materials for forming a functional deposited film, and these compounds (A) and compounds (B
) When introducing an activated halogen that chemically reacts with at least one of the compound (A) and the compound ( B)
are each introduced into the film-forming space through a transport space (B) provided in the transport space (A) and communicating with the film-forming space, and are formed by chemically reacting them. Functional deposited film. RnMm---------------(A)AaBb
−−−−−−−−−−−−−(B) However, m is a positive integer equal to or an integral multiple of the valence of R, and n is a positive integer equal to or an integral multiple of the valence of M. , M is an element belonging to Group II of the periodic table, R is hydrogen (
H), halogen (X), and hydrocarbon group, respectively. a is a positive integer equal to or an integral multiple of the valence of B, n is a positive integer equal to or an integral multiple of the valence of A,
X is an element belonging to Group V of the periodic table, B is hydrogen (H),
Each represents a halogen (X) and a hydrocarbon group. (2) Compound (A) and compound (B) represented by the following general formulas (A) and (B), respectively, which are raw materials used for forming a functional deposited film, and these compounds (A ) and an activated halogen that chemically reacts with at least one of the compound (B) is introduced into a film forming space to form a functional deposited film on a substrate disposed within the film forming space. In the manufacturing method, the activated halogen is introduced into the compound (
A) and the compound (B) are each introduced into the film forming space through a transport space (B) provided in the transport space (A) and communicating with the film forming space. Membrane manufacturing method. RnMm---------------(A)AaBb
−−−−−−−−−−−−−(B) However, m is a positive integer equal to or an integral multiple of the valence of R, and n is a positive integer equal to or an integral multiple of the valence of M. , M is an element belonging to Group II of the periodic table, R is hydrogen (
H), halogen (X), and hydrocarbon group, respectively. a is a positive integer equal to or an integral multiple of the valence of B, n is a positive integer equal to or an integral multiple of the valence of A,
X is an element belonging to Group VI of the periodic table, B is hydrogen (H),
Each represents a halogen (X) and a hydrocarbon group. (3) The method for producing a functional deposited film according to claim 2, wherein the activated halogen is produced in an activation space provided upstream of the transport space (A). (4) The method for producing a functional deposited film according to claim 2, wherein the transport space (A) also serves as an activation space. (5) Production of a functional deposited film according to claim 2, wherein the compound (A) and the compound (B) are excited in advance in an excitation space provided upstream of the transport space (B). Law. (6) The method for producing a functional deposited film according to claim 2, wherein the transport space (B) also serves as an excitation space. (7) The method for producing a functional deposited film according to claim 2, wherein the transport space (B) has a structure that separates and transports the compound (A) and the compound (B). .