KR101567548B1 - Noble Ruthenium compounds, preparation method thereof and process for the thin films using the same - Google Patents

Abstract

The present invention relates to a ruthenium compound represented by the following general formula (1), a method for producing the same, and a method for forming a thin film. The ruthenium compound represented by the following general formula (1) has excellent thermal stability and can form a high quality ruthenium thin film.
[Chemical Formula 1]

Description

[0001] The present invention relates to a ruthenium compound, a method for preparing the same, and a method for forming a thin film using the same,

The present invention relates to a ruthenium compound, a method for producing the same, and a method for forming a thin film using the same.

Ruthenium metals have excellent thermal and chemical stability as well as low resistivity (r _bulk = 7.6 mWcm) and a relatively large work function ( F _bulk = 4.71 eV). In addition, ruthenium metal is excellent in adhesion to copper metal, ruthenium oxide (RuO ₂ ) is not only a conductive oxide having low specific conductivity (r _bulk = 46 mWcm) but also excellent as an oxygen diffusion barrier film, It has excellent stability and is attracting attention as an electrode capacitor material in next generation semiconductor materials such as ferroelectric memory (FeRAM) and dynamic memory (DRAM). Such ruthenium has physical properties that make it a potential gate electrode material for complementary metal oxide semiconductor (CMOS) transistors, such as high melting point, low resistivity, high oxidation resistance and suitable functioning. Indeed, the resistivity of ruthenium is lower than the resistivity of iridium and platinum, making it easier to use for dry etching processes. In addition, ruthenium oxide (RuO ₂ ) has a high conductivity and is composed of oxygen generated from ferroelectric films such as lead zirconate titanate (PZT), strontium bismuth tantalate (SBT), or bismuth lanthanum titanate (BLT) (SRO, SrRuO ₃ ) can also be used as a material of a next-generation semiconductor.

As a conventionally known ruthenium precursor, U.S. Patent Publication No. 2009-0028745 discloses the use of a ruthenium precursor containing nitrogen and two different ligands. In Korean Patent Publication No. 2010-0060482, a benzene ring, a cyclic or acyclic alkene Lt; RTI ID = 0.0 > Ruthenium < / RTI >

However, existing bivalent ruthenium precursors require the development of ruthenium precursors with high thermal stability, chemical reactivity, volatility, and high ruthenium metal deposition rates for atomic layer deposition (ALD) processes.

United States Patent Publication No. 2009-0028745 Korea Patent Publication No. 2010-0060482

It is an object of the present invention to provide a novel ruthenium compound which is thermally stable and which is capable of producing a high-quality ruthenium thin film at a low temperature.

In order to achieve the above object,

The present invention provides a ruthenium compound represented by the following general formula (1).

[Chemical Formula 1]

Each of R ₁ to R ₇ is a linear or branched alkyl group having 1 to 4 carbon atoms.

The present invention also provides a process for preparing a ruthenium compound represented by the above formula (1), wherein a compound represented by the following general formula (2) and (3) is produced by using a metal reducing agent in an alcohol solvent of the general formula (4).

(2)

RuX ₃ aH ₂ O

Wherein X is Cl, Br, or I.

(3)

Each of R ₂ to R ₇ is a linear or branched alkyl group having 1 to 4 carbon atoms.

[Chemical Formula 4]

R ₁ -OH

R ₁ is a linear or branched alkyl group having 1 to 4 carbon atoms.

The present invention also provides a method for growing a ruthenium thin film using the ruthenium compound represented by the above formula (1).

The ruthenium compound of the present invention can be applied to a seed layer for a copper wiring process and can be used as a capacitor electrode and a gate for manufacturing a silicon-based semiconductor device.

1 is an NMR spectrum of the ruthenium compound prepared in Example 1. Fig.
2 is an NMR spectrum of the ruthenium compound prepared in Example 2. Fig.
3 is an NMR spectrum of the ruthenium compound prepared in Example 3. Fig.
4 is an NMR spectrum of the ruthenium compound prepared in Example 4. Fig.
5 is a TGA graph showing the thermal analysis of the ruthenium compound prepared in Example 1. Fig.
6 is an X-ray crystal structure of the ruthenium compound prepared in Example 1. Fig.
7 is an X-ray crystal structure of the ruthenium compound prepared in Example 2. Fig.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a ruthenium compound represented by the following formula (1).

[Chemical Formula 1]

Each of R ₁ to R ₇ is a linear or branched alkyl group having 1 to 4 carbon atoms.

The present invention also provides a process for preparing a ruthenium compound represented by the above formula (1), wherein a compound represented by the following general formula (2) and (3) is produced by using a metal reducing agent in an alcohol solvent of the general formula (4).

(2)

RuX ₃ .xH ₂ O

Wherein X is Cl, Br, or I.

(3)

Each of R ₂ to R ₇ is a linear or branched alkyl group having 1 to 4 carbon atoms.

[Chemical Formula 4]

R ₁ -OH

R ₁ is a linear or branched alkyl group having 1 to 4 carbon atoms.

The reaction for preparing the ruthenium compound of the formula (1) can be represented by the following reaction formula 1, wherein R ₁ of the ruthenium compound of the formula ( ₁₎ is determined according to R ₁ of the alcohol of the formula (4).

[Reaction Scheme 1]

In this reaction, the reactants are used in a stoichiometric equivalent ratio, and zinc is preferably used as the metal reducing agent.

The novel ruthenium compound of Formula 1 of the present invention can form a thin film and can be suitably applied to processes using chemical vapor deposition (CVD) or atomic layer deposition (ALD).

Hereinafter, the present invention will be described in detail with reference to Examples and Experimental Examples.

However, the following examples and experimental examples are illustrative of the present invention, and the present invention is not limited to the following examples.

≪ Preparation of ruthenium compound &

Example  One.

After dissolving 1.0 g of RuCl ₃ xH ₂ O and 1.02 g of 5- (1-methylethylidene) -1,3-cyclopentadiene (6,6-dimethylphenol) in 75 mL of methanol, a metal reducing agent And the mixture was stirred for 12 hours. The reaction solution was filtered to remove by-products under reduced pressure, and recrystallized with hexane to obtain a yellow solid ruthenium compound represented by the following formula (5).

[Chemical Formula 5]

^{_{1 H NMR (C 6 D 6}} , 300MHz): δ 1.38 (CH 3, 6H), 3.04 (OCH 3, 3H), 4.30 (C 5 H 4, 2H), 4.49 (C 5 H 4, 2H)

EA Theoretical value (experimental value): C 57.27 (58.68), H 7.48 (7.46)

Example  2.

The procedure of Example 1 was repeated except that ethanol was used as a solvent to obtain a ruthenium compound represented by the following formula (6) as a yellow solid.

[Chemical Formula 6]

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ 0.94 (CH 2 CH 3, 2H), 1.43 (CH 3, 6H), 3.30 (CH 2 CH 3, 3H), 4.31 (C 5 H 4, 2H _{), 4.52 (C 5 H 4} , 2H)

EA Theoretical value (experimental value): C 59.23 (60.33), H 7.95 (7.14)

Example  3.

The procedure of Example 1 was repeated except that propanol was used as a solvent to obtain a ruthenium compound represented by the following formula (7) as a brown solid.

(7)

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ 0.80 (OCH 2 CH 2 CH 3, 3H), 1.44 (CH 3, 6H), 1.54 (OCH 2 CH 2 CH 3, 2H), 3.66 (OCH 2 _{CH 2 CH 3, 2H),} 4.31 (C 5 H 4, 2H), 4.51 (C 5 H 4, 2H)

Example  4.

The procedure of Example 1 was repeated except that 5- (1-methylpropylidene) -1,3-cyclopentadiene (6-ethyl-6-methylpublen) was used as the pentadienes compound, To obtain a ruthenium compound represented by the formula (8).

[Chemical Formula 8]

^{_{1 H NMR (C 6 D 6}} , 300 MHz): δ 0.96 (CH 2 CH 3, 3H), 1.32 (CH 3, 3H), 1.66 (CH 2 CH 3, 1H), 1.74 (CH 2 CH 3, 1H _{), 3.05 (OCH 3, 3H} ), 4.33 (C 5 H 4, 2H), 4.38 (C 5 H 4, 2H)

Experimental Example  One. Example  1 of the ruthenium compound Thermal analysis

In order to measure the thermal stability, volatility and decomposition temperature of the ruthenium compound, the ruthenium compound of Formula 5 prepared in Example 1 was heated to 900 ° C at a rate of 10 ° C / min, and argon gas was introduced at a pressure of 1.5 bar / Respectively. The pyrolysis did not occur at a mass of 99% up to 134 ° C, but a mass decrease was observed as the temperature was increased to a temperature higher than that, and a mass reduction was 91% at 276 ° C (FIG. 5). Through this, it was confirmed that the T _1/2 is 228 ℃.

Experimental Example  2. Example  1 and Example  2 < / RTI > ray  analysis

In order to confirm the specific structures of the ruthenium compounds of Formulas 5 and 6 prepared in Examples 1 and 2, an X-ray structure was confirmed using a Bruker SMART APEX II X-ray Diffractometer, Respectively.

Claims (4)

A ruthenium compound represented by the following formula (1).
[Chemical Formula 1]

Each of R ₁ to R ₃ is a linear or branched alkyl group having 1 to 4 carbon atoms. A process for preparing a ruthenium compound represented by the formula (1), wherein the compound represented by the following formula (2) and (3) is prepared by using a metal reducing agent in an alcohol solvent of the formula (4).
(2)
RuX ₃ .xH ₂ O
Wherein X is Cl, Br, or I.
(3)

Each of R ₂ and R ₃ is a linear or branched alkyl group having 1 to 4 carbon atoms.
[Chemical Formula 4]
R ₁ -OH
R ₁ is a linear or branched alkyl group having 1 to 4 carbon atoms. A method for growing a ruthenium thin film using the ruthenium compound of the formula (1). 4. The method of growing a ruthenium thin film according to claim 3, wherein the thin film growth process is chemical vapor deposition (CVD) or atomic layer deposition (ALD).

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