JP2004099463A - Method for producing (ro)(r'o)(r"o)m=o, thin film-forming material, thin film and semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for mass-producing high-purity (RO)<SB>3</SB>M=O at a low cost. <P>SOLUTION: (RO)(R'O)(R"O)M [wherein, M is As or P; and R, R' and R" are each an alkyl group and all may be the same or different] is reacted with ozone. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing (RO) (R'O) (R "O) M = O, a thin film forming material, a thin film, and a semiconductor element.
[0002]
[Problems to be solved by the invention]
(RO) (R'O) (R "O) M = O [M is As or P.R] useful as a raw material for doping P or As for semiconductors, a raw material for arsenic glass (AsSG), or an intermediate of an arsenic compound. , R ', R "are alkyl groups. ] Has never been heard of a method for industrially producing high-purity products in large quantities.
[0003]
The following method is known as a method for synthesizing (RO) ₃ M = O.
(1) A method in which bromine acts on (RO) ₃ M.
(2) A method of reacting Ag ₃ MO ₄ with an alkyl iodide.
[0004]
However, in the above method (1), many by-products are generated, and the yield of the target substance (RO) ₃ M = O is very poor. For example, the yield is about 8 to 25%. For this reason, it is not suitable for industrial mass production of high-purity (RO) ₃ M = O.
[0005]
Further, the method (2) is not suitable for industrial mass production because the raw materials used are very expensive. In addition, the yield is as low as 30 to 35%, which is not suitable for mass production of high-purity products industrially.
[0006]
Therefore, an object of the present invention is to provide a technique capable of mass-producing (RO) ₃ M = O with high purity. In particular, it is an object of the present invention to provide a technique for mass-producing high-purity (RO) ₃ M = O at low cost.
[0007]
[Means for Solving the Problems]
As a result of intensive research into solving the above-mentioned problems, it was found that (RO) (R'O) (R "O) M was allowed to react only with ozone (an oxidizing agent containing ozone). RO) (R'O) (R "O) M = O can be obtained.
[0008]
In addition, this method has very few by-products, and can easily remove by-products by distillation, and can easily produce high-purity (RO) (R'O) (R "O) M = O. I also found that I could get it.
[0009]
The invention of the present application has been achieved based on the above findings,
(RO) (R'O) (R "O) M [where M is As or P. R, R 'and R" are alkyl groups, all of which may be the same or different. ] And ozone are solved by a method for producing (RO) (R'O) (R "O) M = O.
[0010]
In particular, (RO) (R'O) (R "O) M [where M is As or P. R, R ', R" are alkyl groups having 1 to 20 carbon atoms, all of which are They may be the same or different. ] And ozone are solved by a method for producing (RO) (R'O) (R "O) M = O.
[0011]
Among them, (RO) (R'O) (R "O) M [where M is As or P. R, R ', R" are alkyl groups having 1 to 8 carbon atoms, all of which are They may be the same or different. ] And ozone are solved by a method for producing (RO) (R'O) (R "O) M = O.
[0012]
The reaction between (RO) (R'O) (R "O) M and ozone is preferably carried out in an inert gas atmosphere, and the reaction can be carried out in a solvent or without using a solvent. But you can.
[0013]
The method of the present invention can obtain (RO) (R'O) (R "O) M = O of considerable purity, but if a higher purity is desired, a simple method called distillation can be used. For example, high purity products having a gas chromatography purity of 99.9% or more can be obtained.
[0014]
Then, a thin film (P-based thin film or As-based thin film) can be formed using (RO) (R'O) (R "O) M = O obtained by the above manufacturing method. (RO) (R'O) (R "O) M = O obtained by the method is transported and decomposed by CVD, and a thin film obtained by doping M [M is As or P] into a Si-based film is obtained. Can be formed. Therefore, (RO) (R'O) (R "O) M = O obtained by the above manufacturing method can be used as a thin film forming material. An As-based thin film, particularly a thin film obtained by doping M in a Si-based film, may be constituted by using (RO) (R'O) (R "O) M = O obtained by the above manufacturing method. I can do it.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for producing (RO) (R'O) (R "O) M = O according to the present invention is as follows: (RO) (R'O) (R" O) M [where M is As or P. R, R 'and R "are alkyl groups, all of which may be the same or different.] And ozone. In particular, (RO) (R'O) (R" O) M [where M is As or P. R, R ', and R "are alkyl groups having 1 to 20 carbon atoms, all of which may be the same or different.] And ozone. Among them, (RO) (R'O ) (R "O) M [where M is As or P. R, R ′, and R ″ are alkyl groups having 1 to 8 carbon atoms, all of which may be the same or different.] And ozone. Ozone O ₃ used is an ozone generator. The gas generated from the ozone generator generates both ozone and oxygen even if only pure ozone is generated, and oxygen containing ozone is supplied, and (RO) (R′O ) (R "O) M may react with ozone. The reaction is performed under an inert gas atmosphere. And a reaction is performed in a solvent. Further, it can be performed without using a solvent. In order to obtain a higher purity product, for example, a high purity product having a gas chromatography purity of 99.9% or more, a distillation operation is performed to remove by-products.
[0016]
The material for forming a thin film according to the present invention, for example, a material for forming a thin film for a semiconductor, particularly a material for forming a thin film for a semiconductor by CVD is (RO) (R'O) (R "O) M obtained by the above-mentioned manufacturing method. = O.
[0017]
The thin film according to the present invention, for example, a semiconductor thin film (P-based film or As-based film) is formed by using (RO) (R'O) (R "O) M = O obtained by the above manufacturing method. In particular, (RO) (R'O) (R "O) As = O is decomposed by CVD, and As is doped into a Si-based film.
[0018]
The semiconductor device according to the present invention, for example, an LSI device has a thin film formed by using (RO) (R'O) (R "O) M = O obtained by the above-mentioned manufacturing method. It has a thin film obtained by doping As into a Si-based film, and (RO) (R'O) (R "O) M = O obtained by the above-mentioned production method was used as the dope material. Things.
[0019]
Hereinafter, a more specific embodiment will be described.
[0020]
【Example】
[Example 1]
100 g of (C ₂ H ₅ O) _{3 As} under an inert gas (argon gas) atmosphere was charged with an ozone generator (O ₃ generating capacity is about 3 g / hour. The gas generated from this generator is O ₃ , O ₂ , and the bubbled with oxygen O ₂ and ozone O ₃ generated by the O ₃ generation amount O ₂ generation amount of it is greater than.). Since the reaction solution generated heat after the start of the injection of ozone or the like, the temperature of the reaction solution was kept at 30 ° C. by cooling the reaction vessel with water, and ozone or the like was blown from the ozone generator for 8 hours.
[0021]
Thereafter, the reaction solution was analyzed by gas chromatography to find that the purity of (C ₂ H ₅ O) ₃ As = O was 97%.
[0022]
Then, by further performing distillation, (C ₂ H ₅ O) ₃ As ＝ O having a purity of 99.9% or more could be obtained. The yield in this case was 91%.
[0023]
Also, when compared with the production cost of (C ₂ H ₅ O) ₃ As = O obtained by the conventional method [method of applying bromine to (RO) ₃ M], the cost of the present invention is as low as 1/10. Was.
[0024]
[Comparative Example 1]
The same operation was performed using an oxygen generator (no ozone was generated, only oxygen was generated) instead of the ozone generator used in Example 1.
[0025]
However, in this case, no reaction occurred, and (C ₂ H ₅ O) ₃ As = O could not be obtained.
[0026]
[Example 2]
In Example 1, the reaction was performed without a solvent. In this example, (C ₂ H ₅ O) ₃ As was dissolved in a hydrocarbon solvent, for example, an octane solvent, and ozone O generated by an ozone generator was added to the solution. _The procedure was performed in the same manner as in Example 1 except that _{3 and the} like were blown.
[0027]
In this example, (C ₂ H ₅ O) ₃ As ＝ O having a purity of 99.9% or more was obtained at a yield of 91%.
[0028]
[Example 3]
The same operation was performed using (CH ₃ O) ₃ As instead of (C ₂ H ₅ O) ₃ As used in Example 1.
[0029]
In this example, (CH ₃ O) ₃ As ＝ O having a purity of 99.9% or more was obtained at a yield of 90%.
[0030]
[Example 4]
(C ₃ H ₇ O) ₃ As was used in place of (C ₂ H ₅ O) ₃ As used in Example 1, and the same operation was performed.
[0031]
In this example, (C ₃ H ₇ O) ₃ As ＝ O having a purity of 99.9% or more was obtained with a yield of 93%.
[0032]
[Example 5]
The same operation was performed using (C ₄ H ₉ O) ₃ As instead of (C ₂ H ₅ O) ₃ As used in Example 1.
[0033]
In this example, (C ₄ H ₉ O) ₃ As ＝ O having a purity of 99.9% or more was obtained with a yield of 89%.
[0034]
[Example 6]
(C ₂ H ₅ O) ₃ As used in Example 1 was replaced with (C ₂ H ₅ O) ₃ P in the same manner.
[0035]
In this example, (C ₂ H ₅ O) ₃ P ＝ O having a purity of 99.9% or more was obtained with a yield of 90%.
[0036]
[Example 7]
The same operation was performed using (CH ₃ O) ₃ P instead of (C ₂ H ₅ O) ₃ As used in Example 1.
[0037]
In this example, (CH ₃ O) ₃ P ＝ O having a purity of 99.9% or more was obtained with a yield of 90%.
[0038]
Example 8
The same operation was performed using (C ₃ H ₇ O) ₃ P instead of (C ₂ H ₅ O) ₃ As used in Example 1.
[0039]
In this example, (C ₃ H ₇ O) ₃ P ＝ O having a purity of 99.9% or more was obtained at a yield of 90%.
[0040]
[Example 9]
The same operation was performed using (C ₄ H ₉ O) ₃ P instead of (C ₂ H ₅ O) ₃ As used in Example 1.
[0041]
In this example, (C ₄ H ₉ O) ₃ P ＝ O having a purity of 99.9% or more was obtained with a yield of 88%.
[0042]
[Example 10]
The Si-As-based oxide thin film using a _{(C 2 H 5 O) 3} As = O obtained in Example 1 was prepared by CVD.
[0043]
The thin film thus obtained is a Si-As-based thin film formed by CVD using (C ₂ H ₅ O) ₃ As = O obtained by a conventional method [a method of allowing bromine to act on (RO) ₃ M]. The film purity and electrical characteristics were much better than the oxide thin film.
[0044]
Therefore, it is considered that an LSI having this Si-As-based oxide thin film (an oxide thin film obtained by doping As into a Si-based film) has high performance.
[0045]
【The invention's effect】
High-purity (RO) ₃ M = O can be mass-produced at low cost.
Further, a high-performance semiconductor device can be obtained.

Claims (11)

(RO) (R'O) (R "O) M [where M is As or P. R, R 'and R" are alkyl groups, all of which may be the same or different. And ozone. (RO) (R'O) (R "O) M = O. (RO) (R'O) (R "O) M [where M is As or P. R, R ', R" are alkyl groups having 1 to 20 carbon atoms, and It may be different. And ozone. (RO) (R'O) (R "O) M = O. The reaction between (RO) (R'O) (R "O) M and ozone is carried out under an inert gas atmosphere, wherein (RO) (R'O) ( R "O) Method for producing M = O. The reaction between (RO) (R'O) (R "O) M and ozone is carried out in a solvent, wherein (RO) (R'O) (R "O) Manufacturing method of M = O. 4. The reaction between (RO) (R'O) (R "O) M and ozone is carried out without solvent, wherein (RO) (R'O) (R "O) Manufacturing method of M = O. The method for producing (RO) (R'O) (R "O) M = O according to any one of claims 1 to 5, wherein the ozone is a gas containing ozone from an ozone generator. The method for producing (RO) (R'O) (R "O) M = O according to any one of claims 1 to 6, wherein a by-product formed in the reaction is removed by distillation. 8. A thin film forming material obtained by the method for producing (RO) (R'O) (R "O) M = O according to any one of claims 1 to 7. (RO) (R'O) (R "O) M = O obtained by the method for producing (RO) (R'O) (R" O) M = O according to any one of claims 1 to 7 A thin film formed using [M is As or P]. (RO) (R'O) (R "O) M = O obtained by the method for producing (RO) (R'O) (R" O) M = O according to any one of claims 1 to 7 Characterized in that M [M is As or P] is doped into a Si-based film. (RO) (R'O) (R "O) M = O obtained by the method for producing (RO) (R'O) (R" O) M = O according to any one of claims 1 to 7 A semiconductor element having a thin film formed by using the method.