JPH0691112B2 - Deposited film formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amorphous or crystalline functional thin film such as a semiconductor film, an insulator film, or a conductor film, particularly an active or passive semiconductor device, or an optical device. The present invention relates to a method for forming a deposited film that is useful for applications such as semiconductor devices, solar cells, and photosensitive devices for electrophotography.

Vacuum deposition method, plasma CVD method, thermal CVD method
Method, photo CVD method, reactive sputtering method, ion plating method and the like have been tried, and in general, plasma CVD method is widely used and commercialized.

However, since the deposited films obtained by these deposited film forming methods are required to be applied to electronic devices and optoelectronic devices that require higher functions, electrical and optical characteristics and repeated use There is room to improve the overall characteristics in terms of fatigue characteristics, usage environment characteristics, and productivity and mass productivity including uniformity and reproducibility.

The reaction process in forming a deposited film by the plasma CVD method that has been generalized in the past is the conventional so-called thermal CVD.
It was much more complicated than the method, and its reaction mechanism was not clear. In addition, there are many formation parameters of the deposited film (for example, substrate temperature, introduced gas flow rate and ratio, formation pressure, high frequency power, electrode structure, reaction vessel structure,
(Exhaust speed, plasma generation method, etc.) and the combination of many of these parameters often cause the plasma to be in an unstable state and have a significant adverse effect on the formed deposited film. In addition, it was difficult to generalize the manufacturing conditions because the parameters peculiar to the device had to be selected for each device.

Depending on the application of the deposited film, it may be necessary to achieve a large area, film thickness uniformity, and film quality uniformity for mass production with reproducibility. In this case, since a large amount of capital investment is required for mass production equipment, the management items for its mass production are complicated, the management allowable width is narrowed, and the adjustment of equipment is delicate, It is pointed out as a problem to be improved.

On the other hand, in the conventional technique by the ordinary CVD method, a high temperature is required, and a deposited film having satisfactory characteristics at a company level has not been obtained.

These problems remain as a larger problem especially when forming a thin film of a II-VI group compound.

As described above, in forming a functional film, it is earnestly desired to develop a method for forming a deposited film, which can ensure practical properties and can be mass-produced by a low-cost apparatus while maintaining uniformity.

〔Purpose〕

The present invention eliminates the above-mentioned drawbacks of the conventional deposited film forming method, and at the same time provides a novel deposited film forming method which does not depend on the conventional forming method.

The object of the present invention is to easily manage the characteristics of the functional film,
A method for forming a deposited film, which maintains at least the characteristics of a high-quality film obtained by the conventional method and simplifies the control of film forming conditions and facilitates mass production of the film while improving the deposition rate. Is to provide.

〔Constitution〕

Another object of the present invention is to provide a deposited film forming method capable of easily forming a good quality II-VI group compound deposited film in which unnecessary impurities such as carbon are hardly found.

An object of the present invention is, in a deposited film forming method for forming a deposited film on a substrate arranged in a film forming space, m is a positive integer which is equal to or a multiple of the valence of R, and the valence of M of n. A non-activated compound (A) represented by the general formula RnMm, where M is an element belonging to Group IIB of the periodic table and R is a hydrocarbon group. , A is a positive integer that is equal to or an integer multiple of B, b is a positive integer that is equal to or an integer multiple of A, and A is a positive integer in the periodic table.
When B, which is an element selected from O, S, Se and Te belonging to Group VI, is hydrogen, halogen or a hydrocarbon group, the compound (B) represented by the general formula AaBb and the above compound Forming a deposited film of a II-VI group compound on the substrate by introducing into the film formation space an activated halogen as an active species generated in an activation space different from the film space and causing a chemical reaction. Is achieved by the method for forming a deposited film.

[Operation] In the method of the present invention, the compound (A) represented by the general formulas (A) and (B) and the compound ( B) and the introduced amount of active species that chemically reacts with at least one of these, the temperature in the substrate and the film formation space,
It becomes the internal pressure in the film forming space, so that the control of the formation of the deposited film is facilitated, and the functional deposited film having reproducibility and mass productivity can be formed.

According to the present invention, the activated halogen facilitates the elimination of the hydrocarbon group and the like from the compounds (A) and (B) leaving the group II element and the group VI element, and the inclusion of unnecessary impurities such as carbon. It is possible to easily form a high-quality II-VI group compound deposited film that is rarely seen.

[Explanation of Preferred Embodiments] The “active species” in the present invention means the compound (A) or /
And causing a chemical interaction with the compound (B) to give energy to the compound (A) or / and (B), or chemically react with the compound (A) or / and (B). Then, the compound (A) and / or (B) has a function of bringing the compound (A) and / or (B) into a state capable of forming a deposited film. Therefore, the “active species” may or may not include a component that constitutes a deposited film to be formed.

The general formulas (A) and (B) used in the present invention
Compounds (A) and (B) represented by each of the above are formed on the substrate by causing a chemical reaction by causing a molecular collision with the active species in the space where the substrate to be formed is present. It is more desirable to select one that spontaneously generates a chemical species that contributes to the formation of a deposited film, but in a normal existence state, it is inactive with the above active species, or When the compounds (A) and (B) have no such activity, the compounds (A) and (B) are replaced by the compounds represented by the general formula (A).
And (B) in which M and A in M are not completely dissociated from each other, and excitation energy having a strength that does not completely dissociate is applied to the compound (A) and (B) to an excited state capable of chemically reacting with the active species. In addition, a compound capable of producing such an excited state is employed as one of the compounds (A) and (B) used in the method of the present invention.

In the present invention, the compound in the excited state will be referred to as “excited species” hereinafter.

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

That is, “M” is an element belonging to Group IIB of the periodic table, specifically Zn, Cd, Hg, and “A” is an element belonging to Group VI of the periodic table from O, S, Se, Te. The elements selected can be mentioned.

“R” and “B” include monovalent, divalent and trivalent hydrocarbon groups derived from linear and side chain saturated hydrocarbons and unsaturated hydrocarbons, or saturated or unsaturated hydrocarbon groups. Mention may be made of monovalent, divalent and trivalent hydrocarbon radicals derived from monocyclic and polycyclic hydrocarbons.

As the unsaturated hydrocarbon group, not only a single type of carbon-carbon bond but also a single type bond, a double bond, and a triple bond have at least two types of bonds. Can be effectively adopted if they are different in achieving the purpose of.

Further, in the case of an unsaturated hydrocarbon group having a plurality of double bonds, it may be a non-integrated double bond or an integrated double bond.

As the acyclic hydrocarbon group, an alkyl group, an alkenyl group,
Alkynyl group, Alkylidene group, Alkenylidene group, Alkynylidene group, Alkyridine group, Alkenyridine group,
Alkynilidine groups and the like can be mentioned as preferable ones, and in particular, those having 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and most preferably 1 to 5 carbon atoms are desirable.

In the present invention, compounds (A) and (B) that are effectively used are selected such that they are gaseous in the standard state or can be easily vaporized under the use environment,
In the selection of "R" and "M" and "A" and "B" listed above, a combination of "R" and "M" and "A" and "B" is selected as desired. It

In the present invention, specific examples that are effectively used as the compound (A) include ZnMe ₃ , CdMe ₃ , ZnEt ₃ and CdEt ₃ that are effectively used as the compound (B). Me ₂ O, Me ₂ S, Me ₂ Se, Me ₂ Te, Et ₂ O, Et ₂ S, Et ₂ Se,
Et ₂ Te, X ₂ O, SX ₂ , SX ₄ , SX ₆ , SeX ₂ , SeX ₄ , SeX ₆ , TeX ₆ H ₂ O, H ₂ S, H
₂ Se, H ₂ Te, etc. can be mentioned.

In the above, X represents halogen (F, Cl, Br, I), Me represents a methyl group, and Et represents an ethyl group.

The life of the active species used in the present invention is preferably short in consideration of the reactivity with the compound (A) and / or (B), and it is easy to handle during film formation and transportation to the film formation space. Considering the above, the longer the better. Further, the life of the active species depends on the internal pressure of the film forming space.

Therefore, the active species used are selected so that the functional film having the desired properties can be effectively obtained in consideration of the production efficiency, and the active species used have an appropriate life in relation to other film forming conditions. The active species having is selected appropriately and used.

The active species used in the present invention has, as its life span,
In view of the above points, the active species having a properly selected life span is appropriately selected as desired from within the range of compatible chemical affinity with the compound (A) or / and (B) specifically used. However, the life is preferably 1 × 10 ⁻⁴ seconds or more, more preferably 1 × 10 ⁻³ seconds or more, most preferably 1 × 10 ¹² seconds or more under the environment of the conforming range of the present invention. Is desirable.

The active species used in the present invention has a function as a so-called initiator (initiater) to be minimized when the chemical reaction with the compound (A) or / and (B) occurs in a chain. As the amount of introduction to the film formation space,
It suffices to secure an amount such that chemical reactions occur efficiently in a chain.

The active species used in the present invention are introduced into the film formation space (A) at the same time when the deposited film is formed in the film formation space (A),
The compounds (A) and (B) or / and the compound (A) G containing a constituent element which is a main constituent of the deposited film to be formed.
Excited species (A) and / or compound (B) excited species (B)
Chemically interact with. As a result, a II-VI group compound deposited film having a desired functional composition is easily formed on a desired substrate.

According to the present invention, the ambient temperature of the film formation space (A) and the substrate temperature are controlled arbitrarily as desired to make it more stable.
It can be a CVD method.

One of the points that the method of the present invention is different from the conventional CVD method is that it is different from the film formation space (A) in advance [activation space (C)].
Is to use the activated species activated in. As a result, the deposition rate can be dramatically increased compared to the conventional CVD method, and in addition, the substrate temperature during deposition film formation can be further lowered, and stable film quality control can be achieved. It is possible to industrially provide a large amount of deposited film having improved film characteristics at low cost.

In the present invention, the active species generated in the activation space (C) are not only activated by being excited by energy of discharge, light, heat or the like or by combination thereof, but also contact with a catalyst or addition thereof. May be generated by

In the present invention, the raw material that is introduced into the activation space (C) to generate the active species is preferably a substance that is in the form of a gas or easily vaporizable and that generates a halogen radical. thereof include _{F 2, Cl 2, Br 2} , I 2 of halogen gas or _{BrF, ClF, ClF 3, ClF} 5, BrF 5, BrF 3, IF 7, IF 5, IC
Examples thereof include interhalogen compounds such as l and IBr, and rare gases such as He and Ar that can be used in addition to these.

Activated species are generated by adding activation energy such as heat, light, or discharge in the activation space (C) to the above. This active species is introduced into the film forming space (A). At this time, it is necessary that the life of the active species is desirably 1 × 10 ₋₄ seconds or more. By having such a life, the deposition efficiency and the deposition rate are accelerated, and the film formation space (A) is formed. Increase the efficiency of the chemical reaction with the introduced compound (A).

The activation energy that causes an activation action on the active species generating substance in the activation space (C) is specifically heat energy such as resistance heating or infrared heating, laser light, mercury lamp light, halogen lamp light, or the like. Energy, microwave, RF, low frequency, electric energy using discharge such as DC, etc. can be mentioned. These activation energies act on the active species generating substance alone in the activation space (C). Also, two or more kinds may be used in combination to act. The compound (A), the compound (B), and the active species introduced into the film formation space (A) cause a chemical reaction due to mutual collision at a molecular level even as they are to deposit a functional film on a desired gas. The compounds that can be selected from those listed above can be selected depending on the selection method of each of the compound (A), the compound (B) and the active species, or In the case where the chemical reaction is performed more effectively and the deposited film is efficiently generated on the gas, it acts on the compound (A), the compound (B), and / or the active species in the film formation space (A). The reaction accelerating energy, for example, the activation energy used in the above-mentioned activation space (C) can be used. Alternatively, in order to bring the compound (A) and the compound (B) into the above-mentioned excited state in the other activation space (B) before being introduced into the film formation space (A). Excitation energy may be applied.

In the present invention, the ratio of the total amount of the compound (A) and the compound (B) introduced into the film forming space (A) and the amount of the active species introduced from the activation space (C) is determined by the deposition conditions, the compound (A). , The type of compound (B) and active species, the desired characteristics of the functional membrane, etc., and may be appropriately determined according to the desire, but 1000: 1 to 1:10 (introduction flow ratio) is suitable, and more preferably 500. -1 to 1: 5 is preferable.

When the active species does not cause a chain chemical reaction with the compound (A) or / and the compound (B), the above introduction ratio is
It is preferably 10: 1 to 1:10, more preferably 4: 1 to 2: 3. The internal pressure of the film formation space (A) during film formation is appropriately determined according to the selected type of compound (A), compound (B) and active species, deposition conditions, etc., but is preferably 1 × 10 ^-2. ˜5 × 10 ³ Pa, more preferably 5 × 10 ⁻² to 1 × 10 ³ Pa, most preferably 1 × 10 ^{−1 to} 5 × 10 ² Pa. Further, when it is necessary to heat the substrate during film formation, the substrate temperature is preferably 50 to 1000.
C., more preferably 100 to 900.degree. C., optimally 100 to 750.degree.

When introducing the compound (A), the compound (B) and the active species into the film forming space (A), the introduction method may be through a transport pipe connected to the film forming space (A). Alternatively, the transport pipe may be extended to near the deposition surface of the substrate installed in the deposition space (A), and the tip may be introduced in the form of a nozzle, and the transport pipe may be doubled. With the tube on the circle side,
The other may be transported by the outer tube, for example, the active species may be transported by the inner tube, and the compound (A) and the compound (B) may be transported by the outer tube and introduced into the film formation space (A).

Further, three nozzles connected to the transport pipe are prepared, and the tips of the three nozzles are arranged in the vicinity of the surface of the substrate already installed in the film forming space (A) so that the surface of the substrate is close to the nozzle. In, the compound (A) and the compound (B) discharged from the respective nozzles and the active species may be mixed and introduced. In this case, the functional film can be selectively formed on the substrate, which is convenient because it can be patterned simultaneously with the film formation.

Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 F ₂ gas 200SCCM was introduced into the activation chamber 103 made of a quartz glass tube through the gas introduction pipe 102 of FIG. 1, and the waveguide placed on the activation chamber 103 as the activation source 5 was introduced. A microwave of 300 W was made to act on the activation chamber 103 from the tube to generate F radicals in the activation chamber 103. The generated F radicals are transferred to the nozzle 100 via a transport pipe 102-2 made of a quartz glass pipe.
-3 was introduced into the film forming chamber 104.

At the same time, the (CH ₃ ) ₂ Zn bubbled by He gas through the gas inlet pipe 101-2 was supplied at a rate of 10 mmol / min to the nozzle 10.
It was introduced into the film forming chamber 104 from 0-2. On the other hand, gas inlet pipe 101-
H ₂ S gas was introduced into the film forming chamber 104 from the nozzle 100-10 at a rate of 10 mmol / min through 1. In this case (C ₂ H ₅ ) ₂ Zn and H ₂ S
Is activated by the action of H radicals to decompose Zn and S, and Al ₂ O ₃ heated to about 230 ° C. by the substrate heater 109.
Approximately 2.2 μm on a substrate of 108 in an area of 30 cm × 30 cm in 1.5 hours
A ZnS film having the film thickness of was formed.

When the film characteristics of this ZnS film were evaluated, it was confirmed that there was no unevenness in the film thickness and that the semiconductor characteristics were of good quality with little dependence on location.

In Example 2 Example _{1 (C 2 H 5) 2} Zn, and a raw material gas shown in Table 1 respectively used to as the compound (A) and the compound (B) in place of H ₂ S, a compound (A) The amount of compound (B) introduced is
The film was formed in substantially the same manner as in Example 1 except that the conditions were 1 mmol / min and the conditions shown in Table 1 were obtained. As a result, the thin film shown in Table 1 was formed.

When the film characteristics of these thin films were evaluated, it was confirmed that the films had a uniform film thickness and were uniform and of excellent quality.

Example 3 In Example 1, an RF discharge device 106 installed around the film forming chamber 104 supplied 3 W of power at a high frequency of 13.56 MHz to the film forming chamber 104 to form a plasma atmosphere in the reaction chamber 104. . In this case, the substrate 106 was placed at a position of about 1 cm on the downstream side of the plasma atmosphere so as not to directly touch the plasma atmosphere. A ZnS film having a thickness of about 2 μm could be formed within 1 hour after starting the film formation. At this time, the substrate temperature was kept at 200 ° C. Except for the above, the same procedure as in Example 1 was carried out.

When the film characteristics of this GaAs film were evaluated in the same manner as in Example 1, it was confirmed that the film was of good quality.

The film was also mechanically excellent without peeling from the substrate.

Example 4 A GaAs film was formed by the same method as in Example 1 except that Cl ₂ gas was used instead of F ₂ gas in Example 1.
It was confirmed that the film characteristics of this GaAs film were also good.

〔The invention's effect〕

According to the deposited film forming method of the present invention, desired electrical, optical, photoconductive and mechanical properties of the formed film are improved, and reproducibility in film formation is improved. Moreover, it is possible to improve the film quality and make the film quality uniform so that the inclusion of unnecessary impurities such as carbon is hardly seen, and it is advantageous for increasing the area of the film, improving the film productivity and mass production. Can be easily achieved.

Further, since the film can be formed at a low temperature, the film can be formed even on a substrate having poor heat resistance. The process can be shortened by the low temperature treatment. The effect that the composition ratio and characteristics can be managed is exhibited.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a manufacturing apparatus embodying the method of the present invention. 101 …… Introduction pipe, 102 …… Transport pipe, 103 …… Activation chamber, 104 …… Film forming chamber.

Front page continuation (72) Inventor Masahiro Kanai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shunri Oda 8-11-14-503 Fukasawa, Setagaya-ku, Tokyo (72) Invention Satoru Shimizu 2-41-21 Fujigaoka, Midori-ku, Yokohama-shi, Kanagawa (56) Reference JP 54-158190 (JP, A) "IBM TDB", 22 [8A], (1980-1) , P .; 3391-2 The 45th "The Society of Biological Society Proceedings" ('84 -10-12), p. 628 ~ 630

Claims (1)

[Claims] 1. A deposition film forming method for forming a deposition film on a substrate arranged in a film forming space, wherein m is a positive integer equal to or an integer multiple of R, and n is a valence of M. A non-activated compound (A) represented by the general formula RnMm, where M is an integer that is equal to or an integer multiple thereof, M is an element belonging to Group IIB of the periodic table, and R is a hydrocarbon group; a is a positive integer that is equal to or an integer multiple of B, b is a positive integer that is equal to or an integer multiple of A, and A is O, S, Se belonging to Group VI of the periodic table. , An element selected from Te,
When B is hydrogen, halogen or a hydrocarbon group, the general formula
A non-activated compound (B) represented by AaBb and an activated halogen as an active species generated in an activation space different from the film formation space are introduced into the film formation space and chemically reacted. A method for forming a deposited film, comprising forming a deposited film of a II-VI group compound on the substrate by: