JPH0472066A - Production of thin film using organic metal complex - Google Patents

Abstract

PURPOSE:To offer the production method of metal thin films which satisfies both of fast film formation and excellent film property by using a metal complex of specified beta-diketone (1,3-diketone) org. compd. CONSTITUTION:In the production process of thin films by vapor phase growing method, a complex of metal and org. compd. expressed by the formula (wherein R is hydrogen or CH3) is used. The org. metal complex to be used is synthesized, for example, from a water-alcohol soln. of 2,6-dimethyl-3,5-heptanedione or 2,2,6-trimethyl-3,5-heptane dione and metal inorg. acid salt (chloride, nitrate, sulfide, etc.,) or metal carboxylic acid salt (formate, acetate, etc.,). The obtd. coarse crystal is washed with water and then with a solvent (n-hexane, benzene, etc.,) and further dried. Thus, beta-diketone-type org. metal complex can be easily obtained.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing thin films using organometallic complexes, and more specifically, to a method for producing a thin film using an organometallic complex, and more specifically, a method for producing a thin film using a specific composition useful as a superconducting material, a translucent ceramic material, an LSI thin film material, etc. The present invention relates to a method for producing a thin film using a metal complex of a specific β-diketone (1,3-diketone)-based organic compound.

[Prior Art] Conventionally, methods for forming single-crystalline and polycrystalline thin films include dry processes and wet processes, but in general, dry processes are frequently used.
Physical deposition methods such as vacuum evaporation, ion blasting and sputtering, and chemical vapor deposition (CVD)
There are chemical film-forming methods such as the CVD method, but the CVD method has two advantages: (1) easy control of film-forming speed;
G) Since high-speed film formation is possible, it is suitable for mass production and is generally in practical use.

Note that thermal CVD, optical CVD, and plasma CVD are employed as the CVD method for forming a metal thin film by decomposing the vapor of an organometallic complex.

Conventionally, the organic moieties (ligands) of organometallic complexes used by sublimation include acetylacetone, dipivaloylmethane, hexafluoroacetylacetone, 1,1.1,2
．． 2-pentafluoro-8゜6-dimethyl-3,5-hexanedione and 1,1゜1.2,2,3.3-heptafluoro-7,7dimethyl-4,6-octanedione are known ( Ru.

[Problems to be Solved by the Invention] However, when a thin film is formed using an organometallic complex consisting of the above-mentioned ligand, it may decompose before a satisfactory thin film can be formed, or the complex may have a low sublimation property. Therefore, there was a problem that a satisfactory thin film formation rate could not be obtained, and as a result, a uniform thin film with good reproducibility could not be easily obtained.

Also, hexafluoroacetylacetone, 1°1.1.
2.2-pentafluoro-8,6-cymethyl-3.5-
Hexanedione, 1. 1. 1. 2゜2.3.3-
When using an organometallic complex having hebutafluoro-7,7-dimethyl-4,6-octanedione as a ligand,
There was also the problem that fluoride was generated during film formation.

Therefore, an object of the present invention is to solve the above-mentioned problems such as decomposition during film formation or generation of fluoride during film formation, and to obtain a homogeneous thin film with good reproducibility at a high film formation rate. The object of the present invention is to find an organometallic complex as a raw material compound and, as a result, to provide a method for producing a thin film that satisfies both high-speed film formation and excellent film properties.

[Means and effects for solving the problem] The present inventors studied various organometallic complexes to achieve the above object, and found that 2,6-dimethyl-3,5-hebutanedione or 2.2.6 When we measured the physical properties of the complex of -drimethyl-3.5-hebutanedione and metal, we found that it was highly sublimable, had a considerable vapor pressure at low and medium temperatures (below 250°C), and had a high evaporation temperature ( Since the decomposition temperature (sublimation temperature) and decomposition temperature are clearly different, and the amount of complex entrained in the inert gas is larger than that of conventional products, high-speed film formation is possible, and the properties of the film formed are also excellent. This heading led to the present invention.

That is, the present invention uses the following general formula, CH300CHI (1) as a raw material compound when manufacturing a thin film by a vapor phase growth method (in the formula, R is either H or CH3). be)
.

The present invention provides a method for producing a thin film characterized by using a complex of an organic compound and a metal represented by:

Further, metals used in the production of the organometallic complex of the present invention include Group IIA elements such as Ca, Sr, and Ba, H
Examples include group A elements, group IVA elements such as Z', and group IB elements such as Cu and Au.

Regarding the organometallic complex used in the present invention, for example, 2.
6-dimethyl-3,5-hebutanedione or 2,2.
6-) Synthesized from a water-alcoholic solution of dimethyl-3,5-hebutanedione and metal inorganic acid salts (chlorides, nitrates, sulfides, etc.) or metal carboxylates (formates, acetates, etc.). By washing the resulting crude crystals with water, washing with a solvent (n-hexane, benzene, etc.), and further drying, a β-diketone organometallic complex can be easily obtained.

The method of the present invention will be described below as an example of a method for producing a thin film using a conventional CVD method, with reference to FIG. 1, which schematically shows an outline of a thermal CVD method.

An inert carrier gas 4 is fed through a flow meter 5 into a raw material container 2 (maintained at a constant temperature of 50 to 250°C) filled with the organometallic complex 1 obtained as described above in a constant temperature bath 3 at a flow rate. is introduced at a rate of 5 to 500 J/win, the organic metal complex raw material is entrained and sublimated, and introduced into a quartz reaction tube 7 provided in a pyrolysis furnace 6, and heated to a predetermined temperature of 250 to 750°C by a heater 8. The organometallic complex is thermally decomposed on the substrate 9 which is heated and held to form a metal thin film. The piping from the raw material container 2 to the pyrolysis furnace 6 was maintained at a temperature of 50 to 250° C. by a heat insulating layer 10 or a heat insulating means to prevent condensation. Further, in the figure, 11 is a cooling trap, 12 is a valve, and 13 is a rotary pump. Note that the arrow indicates the direction in which the sublimated organometallic complex is transferred or the direction in which decomposed gas is discharged.

The β-diketone-based organometallic complex used in the present invention has high sublimability, and the sublimation temperature and decomposition temperature are far apart, and the amount of the complex that is entrained in the inert gas is larger than that of conventional products. Since the film is homogeneous and free of impurities, both excellent film properties and high speed film formation can be achieved by using a β-diketone organometallic complex as a raw material compound.

The present invention will be further explained below with reference to Examples.

[Example 1] The thermal CVD method will be explained with reference to FIG. 1, which schematically shows the outline.

First, 1 g of bis-2,6-dimethyl-3,5-hebutanedionocopper complex is filled into a raw material container 2 (made of glass, maintained at a constant temperature of 100°C), and then argon gas 4 is poured into this container 2 for 200 m, Q/ sin, and bis-2,
The 6-dimethyl-3.5-heptane dionocopper complex was introduced into the thermal decomposition furnace 6.

On the other hand, the silicon substrate 9 installed in the quartz reaction tube 7 of the pyrolysis furnace 6 is heated to 500°C by the heater 8, and the piping from the raw material container 2 to the pyrolysis furnace 6 is heated to 500°C.
It was kept warm.

Under the above conditions, a uniform copper thin film with a thickness of 2,100 wafers was obtained on the substrate 9 after one hour.

[Example 2] Same as Example 1 except that tris-2,6-dimethyl-3,5-hebutanedioyttrium complex was used instead of bis-2,6-dimethyl-3,5-hebutanedionoyttrium complex. When the film was formed using a method, the thickness was 1,000 yen after 1 hour.
700 uniform yttrium thin films were obtained.

[Example 3] After filling 1 g of bis-2,2,6-)dimethyl-35-heptanediono copper complex into a raw material container 2 (made of glass, maintained at a constant temperature of 100°C), argon gas was introduced into this container 2. 200m17m4n of gas was introduced, and bis-2,2,
The 64-rimethyl-3,5-heptane dionocopper complex was introduced into the thermal decomposition furnace 6. On the other hand, the silicon substrate 9 installed in the quartz reaction tube 7 of the pyrolysis furnace 6 is heated to 500°C by the heater 8, and the piping from the raw material container 2 to the pyrolysis furnace 6 is 15 (1' It was kept warm at C.

Under the above conditions, a uniform copper thin film with a thickness of 2.300 mm was obtained on the substrate 9 after 1 hour.

U Example 4.1 Tris-2,26-trimethyl-3.
A film was formed in the same manner as in Example 3 except that a 5-hebutanedioyttrium complex was used, and a uniform yttrium thin film with a thickness of 2,000 mm was obtained after 1 hour.

[Effects of the Invention] As explained above, the organometallic complex used in the method of the present invention is easy to synthesize, has a high vapor pressure, and has a clearly different sublimation temperature and decomposition temperature. When used as a raw material compound when manufacturing metal thin films by this method, it is possible to form thin films at high speed, and there is no generation of fluoride during film formation, and the formed metal film is homogeneous. Since the film has excellent film properties, it is possible to provide a method for producing a thin film that satisfies the excellent film properties and high speed film formation that have not been possible with conventional products.

[Brief explanation of drawings]

Figure 1 shows the method for manufacturing thin films using the normal CVD method.
1 is a schematic cross-sectional view showing an outline of a thermal CVD method. Explanation of symbols 1... Organometallic complex 2... Raw material container 3... Constant temperature bath 4... Inert carrier gas 5... Flow meter 6... Pyrolysis furnace 7 ... Quartz reaction tube 8 ... Heater 9 ... Substrate 10 ... Heat insulation layer 11 ... Cooling trap 12 ... Valve 13 ... Rotary pump patent applicant Same °Wa Mining Co., Ltd.

Claims (2)

[Claims] (1) When manufacturing thin films by the vapor phase growth method, the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc. are used as raw material compounds▼・・・・・・(I
) (wherein R is either H or CH_3). A method for producing a thin film characterized by using a complex of an organic compound represented by the above and a metal. (2) The method for producing a thin film according to claim 1, wherein the central metal of the organometallic complex is a metal element selected from the group consisting of Group IIA metals, Group IIIA metals, Group IVA metals, and Group IB metals of the Periodic Table. .