JP2802676B2 - Method for producing thin film using 1,3-diketone organometallic complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a thin film using an organometallic complex, more specifically, a specific composition useful as a superconducting material, a translucent ceramic material, an LSI thin film material, and the like. The present invention relates to a method for producing a thin film using a metal complex of a specific 1,3-diketone-based organic compound for producing a metal thin film having the same.

[Prior Art] Conventionally, there are a dry process and a wet process as a method of forming a single crystal or polycrystalline thin film.
Dry processes are often used. The dry processes include physical deposition methods such as vacuum deposition, ion plating, and sputtering, and chemical vapor deposition (CV).
There are chemical film formation methods such as D) method, but the CVD method is (1) easy to control the film formation rate, (2) there is no need to perform film formation under high vacuum, (3) high-speed film formation It is generally used in mass production.

The CVD method for decomposing the vapor of the organometallic complex to form a metal thin film includes thermal CVD, optical CVD, and plasma CVD.
The law has been adopted.

Conventionally, the organic portion (ligand) of the organometallic complex used by sublimation includes acetylacetone, dipivaloylmethane, hexafluoroacetylacetone, 1,1,1,2,2
-Pentafluoro-6,6-dimethyl-3,5-heptanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-
4,6-Octanedione is known.

[Problems to be Solved by the Invention] However, when a thin film is formed using an organometallic complex comprising the ligand, the complex may be decomposed before a satisfactory thin film is formed, or the complex may have low sublimability. Because
There was a problem that a satisfactory thin film formation rate could not be obtained, and as a result, a uniform thin film having good reproducibility could not be easily obtained.

Hexafluoroacetylacetone, 1,1,1,2,2
-Pentafluoro-6,6-dimethyl-3,5-heptanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-
When an organometallic complex having 4,6-octanedione as a ligand is used, there is a problem that fluoride is generated during film formation.

Therefore, an object of the present invention is to decompose during film formation,
Alternatively, by solving the above-mentioned problem that fluoride is generated during film formation, an organometallic complex as a raw material compound capable of obtaining a uniform thin film with good reproducibility at a high film formation rate has been found. It is an object of the present invention to provide a method for producing a thin film that satisfies both of the above characteristics and excellent film properties.

Means and Action for Solving the Problems The inventors of the present invention have studied various organometallic complexes in order to achieve the above object, and have found the following specific 1,3-
Physical properties of the complex of the diketone-based organic compound and the metal were measured and found to be highly sublimable.
(0 ° C or less), shows a considerable vapor pressure, and the evaporation temperature (sublimation temperature) is clearly separated from the decomposition temperature. The amount of complex entrained by the inert gas is larger than that of the conventional product, enabling high-speed film formation. In addition, the inventors have found that the characteristics of the film formed thereon are also excellent, and arrived at the present invention.

That is, in the present invention, when producing a thin film by a vapor phase growth method, the following general formula (I)
Another object of the present invention is to provide a method for producing a thin film, comprising using a metal complex having a ligand of a 1,3-diketone organic compound represented by any of (II) and (III).

(R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) The central metal used in the production of the 1,3-diketone-based organometallic complex of the present invention includes II A such as Ca, Sr, and Ba. Group element,
Group IIIA elements such as Y and La, Group IVA elements such as Zr, and Cu and A
Group IB elements such as u can be mentioned.

1,3-diketone organic compounds that provide ligands of organometallic complexes that can be conveniently used in the practice of the present invention include:

A metal complex was synthesized from a water-alcohol solution of the above organic compound and a metal inorganic acid salt (chloride, nitrate, sulfide, etc.) or a metal carboxylate (formate, acetate, etc.), and the obtained crude complex was obtained. After washing the crystals with water, the crystals are washed with a solvent (eg, n-hexane, benzene, etc.), and further dried, whereby a 1,3-diketone-based organometallic complex can be easily obtained.

Hereinafter, the method of the present invention will be described with reference to FIG. 1 schematically showing an outline of a thermal CVD method as an example of a method of manufacturing a thin film by a normal CVD method.

The inert carrier gas 4 is placed in a raw material container 2 (maintained at a constant temperature of 50 to 250 ° C.) in the constant temperature bath 3 and filled with the organometallic complex 1 obtained as described above.
Through the process, the flow rate is adjusted to 5 to 500 ml / min, and the organometallic complex raw material is introduced into the quartz reaction tube 7 provided in the pyrolysis furnace 6 with the sublimation and sublimation. The organic metal complex is thermally decomposed on the substrate 9 which is heated and maintained at 750 ° C. to form a metal thin film. In addition, the piping from the raw material container 2 to the thermal decomposition furnace 6 was kept at a temperature of 50 to 250 ° C. by a heat insulating layer 10 or a heat insulating means in order to prevent condensation. In the figure, 11 is a cooling trap, 12 is a valve, 13
Is a rotary pump. The arrow indicates the direction in which the sublimated organometallic complex is transferred or the direction in which the decomposed gas is discharged.

The 1,3-diketone-based organometallic complex used in the present invention has a high sublimation property, the sublimation temperature and the decomposition temperature are considerably different, the amount of the complex entrained by the inert gas is larger than that of the conventional product, and the film is formed. Since the resulting film is homogeneous and free from impurities, the use of a 1,3-diketone-based organometallic complex as a raw material compound can satisfy both excellent film characteristics and high-speed film formation.

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

Example 1 The thermal CVD method will be described with reference to FIG. 1 schematically showing the outline.

First, bis-5-methyl-2,4-hexanediono copper complex 1
g was filled in a raw material container 2 (made of glass, kept at a constant temperature of 100 ° C.), and then argon gas 4 was introduced into the container 2 at a rate of 200 ml / min, and bis-5-methyl-2,4-hexane was added to the gas. The diono copper complex was entrained and led to the thermal decomposition furnace 6. On the other hand, the silicon substrate 9 placed in the quartz reaction tube 7 of the pyrolysis furnace 6 was heated to 500 ° C. by the heater 8, and the piping from the raw material container 2 to the pyrolysis furnace 6 was kept at 150 ° C. .

Under the above conditions, a uniform copper thin film having a thickness of 2,300 ° was obtained on the substrate 9 after one hour.

[Example 2] A film was formed in the same manner as in Example 1 except that a tris-5-methyl-2.4-hexanedionoytrium complex was used in place of the bis-5-methyl-2,4-hexanedionoy copper complex. However, after 1 hour, a uniform yttrium thin film having a thickness of 1,800 ° was obtained.

Example 3 After charging 1 g of bis-2-methyl-3,5-heptanediono copper complex into a raw material container 2 (made of glass, kept at a constant temperature of 100 ° C.), 200 ml of argon gas 4 was charged into the container 2. min, and the gas was allowed to accompany a bis-2-methyl-3,5-heptanediono copper complex, which was led to a pyrolysis furnace 6. On the other hand, the silicon substrate 9 placed in the quartz reaction tube 7 of the pyrolysis furnace 6 was heated to 500 ° C. by the heater 8, and the piping from the raw material container 2 to the pyrolysis furnace 6 was kept at 150 ° C. .

Under the above conditions, a uniform copper thin film having a thickness of 2,000 mm was obtained on the substrate 9 after one hour.

[Example 4] A film was formed in the same manner as in Example 3 except that a tris-2-methyl-3,5-heptanedionoitrium complex was used instead of the bis-2-methyl-3,5-heptanediono copper complex. After 1 hour, a uniform yttrium thin film having a thickness of 1,600 ° was obtained.

[Example 5] A film was formed in the same manner as in Example 1 except that 1 g of bis-5,5-dimethyl-2,4-hexanedionodicopper complex was used as the organometallic complex. A uniform yttrium thin film of 2,200Å was obtained.

Example 6 As an organometallic complex, tris-5,5-dimethyl-2,4-
Fill a constant temperature bath with 1 g of hexanedionoytrium complex,
When a film was formed in the same manner as in Example 1, a uniform yttrium thin film having a thickness of 1,800 ° was obtained after one hour.

[Example 7] As an organometallic complex, 1 g of bis-2,2-dimethyl-3,5-octanediono copper complex was filled in a thermostat, and a film was formed in the same manner as in Example 1. After one hour, A uniform copper thin film with a thickness of 2,000 mm was obtained.

[Example 8] As an organometallic complex, 1 g of a bis-5-ethyl-2,4-heptanediono copper complex was charged into a constant temperature bath, and a film was formed in the same manner as in Example 1.銅 A uniform copper thin film was obtained.

[Example 9] As an organometallic complex, 1 g of a tris-5-ethyl-2,4-heptanedionoytrium complex was filled in a thermostat, and a film was formed in the same manner as in Example 1.
A uniform yttrium thin film of 2,200Å was obtained.

[Example 10] As an organometallic complex, 1 g of a bis-3-ethyl-4,6-nonanediono copper complex was charged into a thermostat, and a film was formed in the same manner as in Example 1. As a result, a thickness of 2,300 was obtained after 1 hour.銅 A uniform copper thin film was obtained.

[Effects of the Invention] As described above, the 1,3-
Diketone-based organometallic complexes are easy to synthesize, have a high vapor pressure, and have clearly separated sublimation and decomposition temperatures. In this case, it is possible to form a thin film at a high speed, and furthermore, no fluoride is generated during the film formation. A method for producing a thin film that satisfies characteristics and high-speed film formation can be provided.

[Brief description of the drawings]

FIG. 1 shows the thermal C of the thin film manufacturing method by the normal CVD method.
It is a schematic cross section which shows the outline of a VD method. DESCRIPTION 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. Substrate 10… Insulation layer 11… Cooling trap 12… Valve 13… Rotary pump

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-80306 (JP, A) JP-A-63-270313 (JP, A) JP-A-51-141738 (JP, A) (58) Investigation Field (Int.Cl. ⁶ , DB name) C23C 16/00-16/56

Claims (2)

(57) [Claims] (1) When forming a thin film by a vapor phase growth method conducted by introducing a carrier gas,
A method for producing a thin film, comprising using a metal complex having a ligand of a 1,3-diketone-based organic compound represented by any of the following general formulas (I), (II) and (III). (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) 2. The method according to claim 2, wherein the central metal of the organometallic complex is periodic table II.
The method for producing a thin film according to claim 1, wherein the metal element is a metal element selected from the group consisting of a group A metal, a group IIIA metal, a group IVA metal, and a group IB metal.