JPH0474866A - Production of thin film using 1,3-diketone type organometallic complex - Google Patents

Abstract

PURPOSE:To form a thin metallic film having superior characteristics at thigh speed by using a metallic complex of specific 1,3-diketone type organic compound at the time of forming a thin metallic film by a vapor phase epitaxial growth method. CONSTITUTION:At the time of forming a thin metallic film having a specific composition useful for superconducting material, translucency ceramic material, LSI thin film material, etc., on a substrate 9 by a thermal CVD method, the inside of a quartz reaction tube 7 containing the substrate 9 is evacuated by means of a rotary pump 13, and then, a metallic complex 1 which has a ligand consisting of 1,3-diketone type organic compound represented by any of formulae I, II, III and a central metal selected from the group IIA metals of the periodic table, such as Ca, Sr, and Ba, the group IIIA metals, such as Y and La, the group IVA metals, such as Zr, and the group IB metals, such as Cu and Au, and is placed in a raw material vessel 2 in a thermostatic tank 3 held at a constant temp. of 50-250 deg.C is supplied together with an inert carrier gas 4 into the reaction tube 7 and heated, e.g., to 250-750 deg.C by means of a heater 8 and the organometallic complex is thermally decomposed on the substrate 9, by which the thin metallic film can be stably formed.

Description

[Detailed Description of the Invention] [Field of Industrial 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 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 1,3-diketone 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 often used, and try processes include
Physical deposition methods such as vacuum evaporation, ion blasting and sputtering, and chemical vapor deposition (CVD)
Is there a chemical film deposition method such as the CVD method? The CVD method is 0) easy to control the deposition rate, (1) there is no need to perform the deposition under high vacuum, and 3) high-speed deposition is possible. , suitable for mass production and commonly used.

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

Conventionally, organic moieties (ligands) of organometallic complexes used by sublimation include acetylacetone, dipivaloylmethane, hexafluoroacetylacetone, 111,2.2
-Pentafluoro-8゜6-dimethyl-3,5-hexanedione, 1,112.2,3.3-hebutafluoro-
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 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. L 1. 22.3.3-
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] In the process of studying various organometallic complexes to achieve the above object, the present inventors discovered that the following specific 1,3-diketone organic compound and metal When we measured the physical properties of the complex, we found that
Highly sublimable, both at low and medium temperatures (250℃ or less)
It exhibits a considerable vapor pressure, and the evaporation temperature (sublimation temperature) and decomposition temperature are clearly separated, and the amount of complex entrained in the inert gas is larger than that of conventional products, making it possible to form a film at high speed. We discovered that the properties of the resulting film were also excellent.
We have arrived at the present invention.

That is, the present invention provides the following general formula (I), (
The present invention provides a method for producing a thin film characterized by using a metal complex having a 1,3-diketone organic compound represented by either II) or (III) as a ligand.

(R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) CHl (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) 2-methyl-3 5-hebutanedione ・・・・・・(m) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.

2-methyl-3 5-octanedione Also, 1° of the present invention Diketone organometallic complex The central metal used in body manufacturing is Ca.

Sr.

Group IIA elements such as Ba, ■A group elements such as La, Group IVA elements such as Z' and Cu.

IB group such as Au Can list elements.

The 1° diketone organic compounds that provide the organometallic complex 2-methyl-3° nonanedione ligand that can be advantageously used in the practice of the present invention include the following.

H3 Methyl-2 hexanedione (Margin below) methyl 3゜ 5-decanedione 2゜ Dimethyl-3゜ O cutandione CH3 CH3 (that's all (I) Something expressed by the formula.

2.

2-dimethyl-3.

Nonanedione 5.

5-dimethyl-2.

4-hexanedione CH3 CH3 Dimethyl-3.

5-decanedione 2.

Dimethyl-3.

heptanedione CH.

CH.

CH3 (that's all (II) Something expressed by the formula.

(Left below) (11) 5-ethyl 2゜heptanedione (14) 3-ethyl-4,6-zocanedione CH2,
CH.

Ethyl-4 octanedione (15) 3-ethyl-4,6-unzocanedione CH2
・CH3 Ethyl-4゜nonanedione (blank below) CH2 CH3 The above organic compounds and metal inorganic acid salts (chlorides, nitrates,
Synthesize metal complexes from water/alcoholic solutions with metal carboxylates (formates, acetates, etc.) or metal carboxylates (sulfides, etc.).
After washing the obtained crude crystals with water, washing with a solvent (n-hexane, benzene, etc.) and further drying,
1.3-diketone organometallic complexes 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 adjusted to 5 to 500 d/ff1in, and the organometallic complex raw material is entrained and sublimated to be introduced into the quartz reaction tube 7 provided in the pyrolysis furnace 6, and the heater 8
On the substrate 9 heated and maintained at a predetermined temperature of 250 to 750° C., the organometallic complex is thermally decomposed to produce 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 above-mentioned 1,3-diketone-based organometallic complex used in the present invention has high sublimability, and the sublimation temperature and decomposition temperature are considerably different, and the amount of the complex that is entrained in the inert gas is larger than that of conventional products.
And since the formed film is homogeneous and contains no impurities,
, 3-diketone type organometallic complex as a raw material compound, it is possible to satisfy both excellent film properties and high speed film formation.

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

[Example 1 The outline of the thermal CVD method will be explained according to the above-mentioned FIG. 1.

First, 1 g of bis-5-methyl-2,4-hexane diono copper forceps was added to raw material container 2 (made of glass, kept at a constant temperature of 100°C).
After filling the container 2 with 200% argon gas 4,
+ng/min, and bis-5-methyl-
The 2,4-hexanedione copper complex is entrained in the thermal decomposition furnace 6.
led to. 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 kept at 150°C. did.

Under the above conditions, a uniform copper thin film with a thickness of 2.800 mm was obtained on the substrate 9 after one hour.

[Example 2] A product was prepared in the same manner as in Example 1 except that tris-5-methyl-2,4-hexanedioyttrium complex was used instead of bis-5-methyl-2,4-hexanedionoyttrium complex. After 1 hour, a uniform yttrium thin film with a thickness of 1,800 mm was obtained.

[Example 3] 1 g of bis-2-methyl-3,5-heptane dionocopper complex
After filling the raw material container 2 (made of glass, kept at a constant temperature of 100°C), argon gas 4 was added to the container 2 at 20011°C.
1. Q/min, and bis-2 methyl-
The 35-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 kept at 150°C. did.

Under the conditions described above, a uniform thin copper film with a thickness of 2.000 mm was obtained on the substrate 9 after ] hours.

[Example 4] Same method as Example 3 except that tris-2-methyl-3,5-hebutanedioyttrium complex was used instead of bis-2-methyl-3,5-heptansiono copper complex. After 1 hour, a uniform yttrium thin film with a thickness of 1 and 600 layers 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-hexanedionocopper complex was used as the organometallic complex. After 1 hour, the film had a thickness of 2 ,20
A uniform yttrium thin film was obtained.

[Example 6] Tris-5,5-dimethyl-2,
When 1 g of 4-hexanethionoyttrium complex was filled into a constant temperature bath and a film was formed in the same manner as in Example 1, a uniform yttrium thin film with a thickness of 1,800 mm was obtained after 1 hour.

[Example 7] As an organometallic complex, 1 g of bis-2,2-dimethyl 35-octanediono copper complex was filled into a constant temperature bath, and a film was formed in the same manner as in Example 1. After 1 hour, a film with a thickness of 2 ,00
A uniform copper thin film was obtained.

[Example 8] As an organometallic complex, 1 g of bis-5-ethyl-2゜4-heptanedionocopper complex was filled in a constant temperature bath, and a film was formed in the same manner as in Example 1. After 1 hour, the thickness decreased. A uniform copper thin film of 2.5 μm thick was obtained.

[Example 9] As an organometallic complex, 1 g of tris-5-ethyl-2゜4-heptanedioyttrium complex was charged into a constant temperature bath.
When a film was formed in the same manner as in Example 1, a uniform yttrium thin film with a thickness of 2,200 mm was obtained after 1 hour.

[Example 10] As an organometallic complex, 1 g of bis-3-ethyl-4°6-tunandiono copper complex was filled into a constant temperature bath, and a film was formed in the same manner as in Example 1. After 1 hour, a film with a thickness of 2 .300 uniform copper thin films were obtained.

[Effect of the invention] As explained above, 1, 3- used in the method of the present invention
Diketone-based organometallic complexes are easy to synthesize, have high vapor pressure, and have a clear difference in sublimation and decomposition temperatures, so they are used as raw material compounds when producing metal thin films by vapor phase growth. In this case, thin films can be formed at high speed, and fluoride is not generated during film formation, and the formed metal film is homogeneous and has excellent film properties.
It is possible to provide a thin film manufacturing method that satisfies excellent film properties and high speed film formation that have not been found in the past.

[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 gear 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

Claims (2)

[Claims] (1) When producing a thin film by the vapor phase growth method, the following general formulas (I), (II), (III) are used as raw material compounds.
A method for producing a thin film, characterized in that a metal complex having a 1,3-diketone organic compound represented by any of the following as a ligand is used. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・ （
I ) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) ▲There are mathematical formulas, chemical formulas, tables, etc.
I) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・(I
II) (R in the formula represents a lower alkyl group having 1 to 5 carbon atoms.) (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 a group IIA metal, a group IIIA metal, a group IVA metal, and a group IB metal of the periodic table. .