JPH01257194A - Production of thin single crystal film - Google Patents

Abstract

PURPOSE:To easily obtain a thin single crystal film with good reproducibility at a high film forming rate by using the complex of specified org. fluorine compd. and metal as a raw compd. at the time of producing a thin single crystal film by the chemical vapor deposition of an organometal. CONSTITUTION:An org. compd. expressed by formula I (R is 1-4C fluorinated lower alkyl) and an aq. soln. of a metallic compd. (e.g., barium chloride) such as a metal hydroxide and a metallic salt are mixed, the pH is regulated to deposit a crystal, and the crystal is recrystallized to produce the complex (shown by formula II) of the compd. of formula I and a metal. The complex is used as the raw material, and a thin single crystal film is produced by the chemical vapor deposition of an organometal. Since the complex has a high vapor pressure, the thin film can be formed at a high rate. When the complex of the compd. of formula I and Ba, the complex with Y, and the complex with copper are jointly used as the raw material, a Y-Ba-Cu-O based thin ceramic film can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a single crystal thin film using a novel organometallic complex.

[Prior art and its problems]

[Prior art and its problems] Various methods have been known to form three single-crystal films, but organic metal vapor is sent to a thermal scraping furnace with gas entrainment and is thermally decomposed on a substrate. The so-called metal organic chemical vapor deposition method is used to form thin films.
c CheIlical Vapor Deposit
ion (MOCVD method) is commonly used because it is easy to control the thin film formation rate, it can be manufactured near normal pressure, and it is easy to mass-produce.

Conventionally, acetylacetone, hexafluoroacetylacetone, dipivaloylmethane, or cyclopentadiene has been known as an organic moiety (ligand) of a sublimable organometallic complex. However, when using the above-mentioned ligands, there are problems such as difficulty in synthesis and isolation, or the organometallic complex itself may not have the vapor pressure due to decomposition, etc., or the vapor pressure is low and the thin film formation rate is slow. There was a point.

[Means for solving problems]

The present inventors investigated various organometallic complexes and found a method for producing a single crystal thin film that solved the above-mentioned problems.

The present invention provides the following general formula C
I), CH.

! R-C-CH2-C-C-CH3f:I):i
it 1 o OCH.

[In the formula, R represents a fluorinated lower alkyl group having 1 to 4 carbon atoms] A complex of an organic compound and a metal is used.

R in the general formula CI] is a trifluoromethyl group (hereinafter abbreviated as TPM), a pentafluoroethyl group (hereinafter abbreviated as PPM), a heptafluoropropyl group (
Examples include fluorinated lower alkyl groups having 1 to 4 carbon atoms, such as HPM (hereinafter abbreviated as HPM).

The central metal or genus of the organometallic complex of the present invention is not particularly specified; for example, elements of group IIA of the periodic table such as Ca, Sr, and Ba, Y, group B elements such as lanthanum, Cu, Au, etc. Examples include IB group elements such as Bi, VA group elements such as Bi, and mA group elements such as T1.

As a method for producing the above-mentioned organometallic complex, techniques for producing ordinary metal complexes can be adopted. It can be easily obtained by recrystallizing the crude crystals obtained by HL% adjustment from ethanol-water and further drying.

A normal MOCVD technique can be used to manufacture the single crystal thin film. For example, in the production of a single crystal thin film made of a metal oxide, a carrier gas is introduced into a supply container filled with a raw material organometallic complex, and the organometallic complex is introduced into a pyrolysis furnace. This can be carried out by supplying oxygen to the heated substrate for producing a single crystal thin film from a nozzle provided near the substrate, and oxidizing and thermally decomposing the organometallic complex introduced into the thermal decomposition furnace.

Below is an example of the method for producing a single crystal thin film according to the present invention.
-The method for producing a Ba-Cu-0 ceramic thin film will be described in detail.

BaOPPMtf body represented by the following general 2 (n), [hereinafter abbreviated as Ba(PPM)z], PPM complex of Y [
Hereinafter, abbreviated as Y (PPM)] and PPM of Cu
The RF body [hereinafter abbreviated as Cu(PPM)z] is filled into each supply container, and the supply amount of each organometallic complex is adjusted by controlling the temperature of each supply container and the carrier gas flow rate. The organic material introduced into the thermal decomposition furnace is introduced into the thermal decomposition furnace in which the substrate is placed, and oxygen is supplied to the heated substrate for single-crystal three-layer production from a nozzle installed near the substrate. A Y-Ba-Cu-0 ceramic thin film can be produced by subjecting a metal complex to oxidative thermal decomposition.

Although the temperature control of each supply container differs depending on the type of raw material organometallic complex, etc., it is practically controlled at a temperature of 80 to 300°C since the vapor pressure of the raw material organometallic complex is relatively low. Inert gas as carrier gas,
For example, argon, nitrogen, etc. are used. The gas flow rate varies depending on the type of raw material, but is usually 1 to 50.
A gas flow rate of 0 m/min is selected. Note that the piping from the supply container to the pyrolysis furnace is preferably kept warm in order to avoid problems such as 'a shrinkage'. The temperature of the substrate for producing a single crystal thin film is usually preferably about 300 to 700°C. Further, the oxygen supply rate is preferably 1 to 100 R1/min.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example I Y (P PM) s , B a (P PM) z and Cu (PPM) 2 were each filled in a stainless steel container, and a substrate was placed using argon gas with these organometallic complexes as the accompanying gas. It was introduced into a cracking furnace.

The (100) plane of 5rTiOa was used as the substrate, and the substrate was heated to 650°C by a W-wire heater. Oxygen gas jet nozzles were placed at two locations on both sides of the substrate, and oxygen gas was sprayed directly onto the substrate. . The oxygen gas flow rate at this time is 20
It was set as af/rain. YSBa.

Each container containing Cui bodies is heated to 140°C12
They were heated to 20°C and 10"0°C, and argon entrained gas was passed through them at a rate of 100 rail/min. The temperature was kept at about 230"C to avoid condensation of organic metals during the pass to the pyrolysis furnace. did.

When the thin film thus obtained with a thickness of 3,000 yen was heated in oxygen at 406° C. for 30 minutes, it showed zero electrical resistance at 90° C. As a result of analysis by X-ray diffraction, only the peak from the (0041) plane was observed, indicating that the thin film was an oriented single-crystal triple film.

Example 12 A thin film was produced in the same manner as in Example 1 except that Ba(TPM)z was used instead of Ba(PPM)z.

The obtained thin film exhibited zero electrical resistance at 90°C.

Example 3 B a (HPM) z was used instead of Ba (PPM) z, and the flow rate of nitrogen gas entrained in the Ba salt was 140 m/w.
A thin film was produced in the same manner as in Example 1, except that the film was made in the same manner as in Example 1. The obtained thin film showed zero electrical resistance at 90K.

[Effects of the Invention] The organometallic complex of the present invention is easy to synthesize and has a high vapor pressure, so when it is used as a raw material compound in producing a single crystal thin film by organometallic chemical vapor deposition method, The formation speed is high, and single crystal thin films can be easily produced with good reproducibility.

Patent applicant Ube Industries Co., Ltd. Procedural amendment (voluntary) Commissioner of the Japan Patent Office April 1988
Patent application λ filed on June 6th Name of the invention Method for manufacturing single crystal thin film 3 Relationship with the case of the person making the amendment Patent applicant Zip code 755 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Invention of the specification Detailed Explanation Column 5, Contents of Correction (1) Page 6, lines 13 to 15, the statement "It is preferable to keep the supply container... warm" has been changed to "It is preferable to keep the supply container warm." In order to avoid problems such as condensation of the raw material organometallic complex, it is preferable to keep the piping up to the decomposition furnace and the inner wall of the pyrolysis furnace at a temperature lower than the decomposition temperature of the organometallic complex.The preferred insulating temperature is 70 to 250°C. It is.”
Correct to.

(2) Add "and inner wall of pyrolysis furnace" between "bus on the way" and "organic metal at" on page 7, line 15.

that's all

Claims (1)

[Claims] When producing a single crystal thin film by organometallic chemical vapor deposition, the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc. are used as raw material compounds▼ [In the formula, R is carbon number 1] A method for producing a single-crystal thin film, characterized by using a complex of an organic compound represented by -4 fluorinated lower alkyl group] and a metal.