KR102618936B1 - New Ruthenium organometallic compound, and method for producing same - Google Patents

Abstract

The present invention relates to a novel ruthenium organometallic compound that has improved thermal stability and is liquid at room temperature, enabling the production of high-quality ruthenium thin films even at low temperatures, and a method for producing the same.

Description

New Ruthenium organometallic compound and method for producing same}

The present invention relates to a novel ruthenium organometallic compound useful as a raw material for manufacturing semiconductor devices and a method for producing the same.

Ruthenium is useful as an electrode material because not only ruthenium itself but also its oxide has electrical conductivity, and it also has excellent micronization processability. Due to the stable electrode characteristics and excellent processability of ruthenium, ruthenium is being used as an electrode material for miniaturization of memory cells due to the high integration of semiconductor memory devices. In particular, ruthenium thin films are used as electrode materials for DRAM capacitors, which are highly integrated memory devices, or as diffusion barriers for copper wiring materials in semiconductor devices.

Meanwhile, chemical vapor deposition (CVD) or atomic layer deposition (ALD) is used as a method of manufacturing ruthenium-containing thin films for highly integrated memory devices.

In particular, as an organometallic compound for forming a ruthenium thin film or ruthenium oxide thin film by the CVD method, a compound that is liquid at room temperature, has excellent handling properties, and can be supplied stably in terms of stability and vapor pressure is more likely to form a ruthenium thin film or ruthenium oxide thin film. It is advantageous for use.

In addition, since the ruthenium thin film process is achieved by high-temperature thermal decomposition of ruthenium organometallic compounds, compounds with high temperature stability and less residual substances after thermal decomposition are more likely to be excellent ruthenium organometallic compounds for forming ruthenium thin films.

Therefore, ruthenium organometallic compounds suitable for the above conditions are required.

Patent Document 1: Domestic Patent Publication No. 10-0958332 Patent Document 2: Japanese Patent Publication No. 2012-0120182

The present invention is advantageous for forming ruthenium thin films as described above, has excellent thermal stability, has a melting point of 100°C or lower, or is liquid even at room temperature, enabling a stable supply of ruthenium compounds required for the ruthenium thin film formation process, making it relatively easy to use. The purpose is to provide a novel ruthenium organometallic compound and a method for producing the same that enable the easy production of high-quality ruthenium thin films even at low temperatures.

In order to achieve the above object, the present invention provides a ruthenium organometallic compound of the following formula (1).

[Formula 1]

In Formula 1, R is hydrogen or a straight or branched alkyl group having 1 to 4 carbon atoms, and a preferred alkyl group is a methyl group.

Additionally, the present invention provides a method for producing a ruthenium organometallic compound comprising steps 1-1 to 1-4 of (a) to (d) below.

(a) Step 1-1 of obtaining dichloro(cycloheptatriene)ruthenium(II)-dimer from ruthenium chloride hydrate and 1,3,5-cycloheptatriene;

(b) Ditrifluoromethanesulfonate (cycloheptatriene) from dichloro(cycloheptatriene)ruthenium(II)-dimer and silver trifluoromethanesulfonate (Ag(OTf)) in step 1-1. Step 1-2 of preparing ruthenium (II)-dimer;

(c) Trifluoromethane sulfonate (cycloheptatriene) from ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II)-dimer and 2,3,4,5-tetramethyl pyrrole in step 1-2 N) Steps 1-3 for producing (2,3,4,5-tetramethylpyrrole)ruthenium(II); and

(d) trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) and lithium aluminum tri (t-butoxy) hydride (LiAl) of steps 1-3 Steps 1-4 to obtain Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) from (O ^t Bu) ₃ H);

Ru(η ⁵ -CHeptD) and (η ⁵ -NC ₄ Me ₄ ) in steps 1-4 are Ru(η ⁵ -cycloheptadiene) and (η ⁵ -2,3,4,5-tetramethylpyrrole, respectively. )am.

As an example of the present invention, the preparation method of steps 1-1 to 1-4 below is performed when R in the ruthenium organometallic compound of Formula 1 is hydrogen, that is, Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ This is a schematic showing the specific manufacturing method of Me ₄ ).

(Step 1-1)

(Step 1-2)

(Steps 1-3)

(Steps 1-4)

The present invention also provides that, when R in the ruthenium organometallic compound of Formula 1 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, steps 2-1 to 2-4 of steps (i) to (iv) below A method for producing a ruthenium organometallic compound is provided.

(i) Step 2-1 of obtaining dichloro(R-cycloheptatriene)ruthenium(II)-dimer from ruthenium chloride hydrate and R-1,3,5-cycloheptatriene;

(ii) Ditrifluoromethanesulfonate (R-cycloheptatriene) from dichloro(R-cycloheptatriene)ruthenium(II)-dimer and silver trifluoromethanesulfonate (Ag(OTf)) in step 2-1. Step 2-2 of producing heptatriene) ruthenium (II)-dimer;

(iii) Trifluoromethanesulfonate (R -Step 2-3 of producing cycloheptatriene)(2,3,4,5-tetramethylpyrrole)ruthenium(II); and

(iv) trifluoromethanesulfonate (R-cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) and lithium aluminumtri (t-butoxy) hydride ( Steps 2-4 to obtain Ru(η ^{5 -R} CHeptD)(η ⁵ -NC ₄ Me ₄ ) from LiAl(O ^t Bu) ₃ H);
“Ru(η ^{5 -R} CHeptD)(η ⁵ -NC ₄ Me ₄ )” in step 2-4 is “Ru(η ⁵ -R-cycloheptadiene)(η ⁵ -2,3,4,5- tetramethylpyrrole),
R in steps 2-1 to 2-4 is a straight or branched alkyl group having 1 to 4 carbon atoms.

The following production method is a specific production method of Ru(η ^{5 -Me} CHeptD)(η ⁵ -NC ₄ Me ₄ ) when R is a methyl group in the ruthenium organometallic compound of Formula 1 as another embodiment of the present invention. am.

(Step 2-1)

(Step 2-2)

(Step 2-3)

(Steps 2-4)

The ruthenium organometallic compound of the present invention is a novel compound, has excellent thermal stability, and is liquid at 100°C or below or at room temperature, making it possible to easily produce high-quality ruthenium thin films even at low temperatures, making it easy to handle in the manufacturing process of ruthenium thin films. It has excellent advantages.

Figure 1 shows NMR of the product of step 1 of Example 1 of the method for producing the ruthenium organometallic compound of the present invention.
Figure 2 is NMR of the product of step 3 in Example 1 of the method for producing the ruthenium organometallic compound of the present invention.
Figure 3 shows the product of step 4 in Example 1 of the method for producing the ruthenium organometallic compound of the present invention, Ru(η ⁵ -CHeptD)(η ⁵ - This is the NMR of NC ₄ Me ₄ ).
Figure 4 is TGA DATA of Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), a ruthenium organometallic compound in Example 1 of the present invention.
Figure 5 is a differential scanning calorimetry (DSC) of Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), a ruthenium organometallic compound in Example 1 of the present invention.
Figure 6 is an X-ray crystal structure of Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), a ruthenium organometallic compound in Example 1 of the present invention.
Figure 7 is the NMR of isomer-1 in the product of step 3 of Example 2 of the method for producing the ruthenium organometallic compound of the present invention.
Figure 8 is the NMR of isomer-2 in the product of step 3 of Example 2 of the method for producing the ruthenium organometallic compound of the present invention.
Figure 9 shows the product of step 4 in Example 2 of the method for producing the ruthenium organometallic compound of the present invention, Ru(η ⁵ - ^Me CHeptD of isomer-1, a ruthenium organometallic compound in which R in Formula 1 of the present invention is a methyl group. )(η ⁵ -NC ₄ Me ₄ ) NMR.
Figure 10 shows the product of step 4 in Example 2 of the method for producing the ruthenium organometallic compound of the present invention, Ru(η ⁵ - ^Me CHeptD of isomer-2, a ruthenium organometallic compound in which R in Formula 1 of the present invention is a methyl group. )(η ⁵ -NC ₄ Me ₄ ) NMR.
Figure 11 is TGA DATA of Ru(η ^{5 -Me} CHeptD)(η ⁵ -NC ₄ Me ₄ ), a ruthenium organometallic compound (mixture of isomers 1 and 2) of Example 2 of the present invention.
Figure 12 is a differential scanning calorimeter (DSC) at high temperature of Ru(η ^{5 -Me} CHeptD)(η ⁵ -NC ₄ Me ₄ ) (mixture), a ruthenium organometallic compound in Example 2 of the present invention.
Figure 13 is a photograph showing a ruthenium thin film formed by the ruthenium organometallic compound of Example 1 of the present invention.
Figure 14 is the TGA DATA of Ludens, a conventionally known ruthenium organometallic compound.
Figure 15 is a differential scanning calorimeter (DSC) at high temperature of Ludens, a conventionally known ruthenium organometallic compound.

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

[Formula 1]

In Formula 1, R is hydrogen; or a straight-chain or branched alkyl group having 1 to 4 carbon atoms; a preferred alkyl group is a methyl group.

The method for producing the ruthenium organometallic compound represented by Formula 1 of the present invention includes steps 1-1 to 1-4 of (a) to (d) below.

(a) Step 1-1 of obtaining dichloro(cycloheptatriene)ruthenium(II)-dimer from ruthenium chloride hydrate and 1,3,5-cycloheptatriene;

(b) Ditrifluoromethanesulfonate (cycloheptatriene) from dichloro(cycloheptatriene)ruthenium(II)-dimer and silver trifluoromethanesulfonate (Ag(OTf)) in step 1-1. Step 1-2 of preparing ruthenium (II)-dimer;

(c) Trifluoromethane sulfonate (cycloheptatriene) from ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II)-dimer and 2,3,4,5-tetramethylpyrrole in step 1-2 ) (2,3,4,5-tetramethylpyrrole) steps 1-3 for producing ruthenium (II); and

(d) trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) and lithium aluminum tri (t-butoxy) hydride (LiAl) of steps 1-3 Steps 1-4 to obtain Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) from (O ^t Bu) ₃ H);

Ru(η ⁵ -CHeptD) and (η ⁵ -2,3,4,5-NC ₄ Me ₄ ) in steps 1-4 are Ru(η ⁵ -cycloheptadiene) and (η ⁵ -2,3, respectively) , 4,5-tetramethylpyrrole).

The following production method, which is a specific example of the production method of the present invention including steps 1-1 to 1-4 of (a) to (d), is when R in the ruthenium organometallic compound of Formula 1 is hydrogen, that is, A specific method for producing Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) includes the following steps 1-1 to 1-4.

(Step 1-1)

(Step 1-2)

(Steps 1-3)

(Steps 1-4)

Looking specifically at an embodiment of the present invention, in step 1-1, first, ruthenium chloride hydrate (RuCl3.xH2O, 37%) and 1,3,5-cycloheptatriene (1,3,5-cycloheptatriene, After dissolving CHT) in the primary solvent, the air in the solvent mixture is removed using nitrogen gas. The solvent mixture from which the air has been removed is heated to reflux and then cooled to room temperature, the insoluble solid in the solvent mixture is allowed to settle, and the supernatant is removed. After adding a secondary solvent to the solid and stirring, the insoluble solid is allowed to settle, and the supernatant is removed using a cannula. The solid was filtered, washed with a second solvent, and dried to produce [Ru(CHT)Cl ₂ ] ₂ (Dichloro(cycloheptatriene)ruthenium(II)-dimer, the product of step 1-1 as a brown solid. Heptatriene) ruthenium (II) -dimer) is obtained (see Figure 1).

In step 1-1, the amount of 1,3,5-cycloheptatriene (CHT) used relative to the ruthenium chloride hydrate (RuCl3.xH2O, 37%) is 1:2.1 to 1: It is 2.4 (molar ratio).

The first solvent is an alcohol, preferably ethanol, and the amount used is ruthenium chloride hydrate (RuCl3.xH2O, 37%) and 1,3,5-cycloheptatriene (CHT). ) is 2 to 10 times the total amount (parts by weight) used, preferably 2 to 6 times. In the above range, the reaction yield is excellent.

The second solvent is a solvent with lower polarity than the first solvent, and is preferably ether, more preferably diethyl ether.

The reflux heating time of the solvent mixture is 60 to 90 hours, preferably 70 to 90 hours, but the heating time may be determined depending on the amount of reactant used.

Washing with the second solvent is repeated until the color of the second solvent becomes colorless after washing, and the amount of the second solvent used in one washing is 0.2 to 0.3 times the amount of the first solvent used (weight ratio) )am.

In step 1-2, ditrifluoromethane sulfonate (cycloheptatriene) is obtained from dichloro(cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)Cl ₂ ] ₂ ) obtained in step 1-1. ) This is the step of producing ruthenium (II)-dimer ([Ru(CHT)(OTf) ₂ ] ₂ ).

Specifically, dichloro(cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)Cl ₂ ] ₂ ) and silver trifluoromethanesulfonate (Ag(OTf)) obtained from step 1-1 in the glove box. ) is mixed in a reaction vessel, then a third solvent is added to the reaction vessel under nitrogen to dissolve the reactant and stirred at room temperature.

After stirring is completed, the reaction mixture is filtered through a filter, and the remaining solid is washed using the third solvent. The washing is performed until the washing liquid of the third solvent becomes colorless. The washed solid filtrate is dried in vacuum to form a dark brown solid. N) Ruthenium(II)-dimer (Difluoromethanesulfonate(cycloheptatriene)ruthenium(II)-dimer, [Ru(CHT) (OTf) ₂ ] ₂ ) is obtained.

In step 1-2, the amount of silver trifluoromethanesulfonate (Ag(OTf)) used for the dichloro(cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)Cl ₂ ] ₂ ) is 1. :4.0~1:4.2 (molar ratio).

The third solvent is a polar solvent that does not mix with water, and is preferably methylene chloride (CH ₂ Cl ₂ ), and the amount used is ruthenium chloride hydrate (RuCl3.xH2O, 37%) and 1,3,5-cyclo It is 3 to 10 times, preferably 6 to 10 times, the total amount (parts by weight) of heptatriene (1,3,5-cycloheptatriene, CHT). In the above range, the reaction yield is excellent.

The room temperature stirring time for the solvent mixture is 12 to 36 hours, preferably 20 to 30 hours, but is not limited to the above stirring time. The stirring time may proceed until the formation of the complex, which is the product of step 2, is completed, and may also be determined depending on the amount of reactant used.

Washing with the third solvent is repeated until the filtrate, which is the third solvent, becomes colorless after washing.

Step 1-3 is from ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II) -dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) obtained in step 1-2 to trifluoro. This is the step of producing methanesulfonate (cycloheptatriene) (tetramethylpyrrole) ruthenium (II) [Ru(CHT)(η ⁵ -NC ₄ Me ₄ )] (OTf).

Specifically, ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II) -dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) and 2,3,4,5- obtained in steps 1-2 above. After putting tetramethylpyrrole into each reaction vessel 1 and 2 in the glove box, the ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II)-dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) and 2,3,4,5-tetramethylpyrrole, respectively, were taken out from the glove box and dissolved in the third solvent under nitrogen. 2,3,4,5-tetramethylpyrrole from reaction vessel 2 dissolved in the third solvent was mixed with ditrifluoromethanesulfonate (cycloheptatriene)ruthenium(II) dissolved in the third solvent using a cannula. -Move the dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) into reaction vessel 1. At this time, a slight exothermic reaction is observed. After the mixture of reaction vessels 1 and 2 is stirred in a dark room at room temperature, a portion of the third solvent in the mixture is removed using a vacuum.

After removing impurities from the residue from which part of the third solvent was removed using neutral alumina and a primary eluent, the solvent of the eluent was removed under vacuum to remove the product remaining in the neutral alumina using a secondary eluent. A sticky brown solid was obtained. The sticky brown solid was recrystallized using the third solvent to form a yellow-brown solid trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) [Ru(CHT) (η ⁵ -NC ₄ Me ₄ )](OTf) is obtained (see Figure 2).

In steps 1-3, the amount of 2,3,4,5-tetramethylpyrrole used for the (cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) is 1:2.0~ The molar ratio is 1:2.3.

The third solvent may be the same as the solvent in step 2, but other solvents may be used as needed.

The amount of the third solvent added to reaction vessel 1 of the ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II)-dimer ([Ru(CHT)(OTf) ₂ ] ₂ ) is ditrifluoro, which is the reactant. The amount used may be 10 to 40 times (by weight) the amount of methanesulfonate (cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)(OTf) ₂ ] ₂ ). Preferably, it may be 20 to 30 times, but may be determined depending on the amount of the reactant used.

The amount of the third solvent added to the 2,3,4,5-tetramethylpyrrole reaction vessel 2 may be 10 to 30 times (weight ratio) the amount of 2,3,4,5-tetramethylpyrrole used as a reactant. Preferably, it may be 10 to 25 times, but may be determined depending on the amount of the reactant used.

The time taken to transfer the reactants from reaction vessel 2 to reaction vessel 1 may be about 10 to 30 minutes, but may be determined depending on the amount of reactants used. However, the transfer must be determined within a time period in which only a slight exothermic reaction is observed.

The stirring time in the dark room is 12 to 36 hours, preferably 20 to 30 hours, but the stirring time may be determined depending on the amount of reactant used.

Partial removal of the third solvent in the reaction mixture is carried out to the extent of leaving 0.01 to 0.2 (weight ratio) of the total amount of the third solvent used in reaction vessels 1 and 2.

The first eluent is ethyl acetate, and the second eluent is a mixture of CH2Cl2/MeCN.

Finally, steps 1-4 are steps for obtaining Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), which is the ruthenium organometallic compound of the present invention of Formula 1 (when R is hydrogen), Trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) obtained in 1-3 [Ru(CHT)(η ⁵ -NC ₄ Me ₄ )]( OTf) and lithium aluminum tri(t-butoxy) hydride (LiAl(O ^tBu ) ₃ H) were placed in each different reaction vessel within the glove box, and then placed in each different reaction vessel taken out of the glove box. The trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) [Ru(CHT) (η ⁵ -NC ₄ Me ₄ ) was obtained by adding an ether solvent under nitrogen. ](OTf) and lithium aluminum tri(t-butoxy) hydride (LiAl(O ^t Bu) ₃ H) are dissolved.

Lithium aluminum tri(t-butoxy) hydride (LiAl(O ^t Bu) ₃ H) located in one of the reaction vessels above was reacted with the trifluoromethanesulfonate (cycloheptatriene) using a cannula. Transfer to another reaction vessel where (2,3,4,5-tetramethylpyrrole)ruthenium(II) [Ru(CHT)(η ⁵ -NC ₄ Me ₄ )](OTf) is located. At this time, a slight exothermic reaction is observed. After the mixture in the reaction vessel is stirred at room temperature, the ether solvent in the mixture is removed using vacuum. The red solid from which the solvent has been removed is extracted using a first non-polar solvent, and the filtrate is filtered through alumina. The alumina layer is washed using the first non-polar solvent until the filtrate becomes colorless to obtain a filtrate. The yellow solid obtained by removing and concentrating the first non-polar solvent of the extract and filtrate by vacuum is dissolved in a minimum second non-polar solvent and recrystallized at -30°C or lower, preferably -40°C or lower, and the obtained solid is - Washed with the second non-polar solvent at 60°C or lower, preferably -70°C or lower, and then vacuum dried to produce Ru(η ⁵ -CHeptD) (when R is hydrogen), a yellow ruthenium organometallic compound of Formula 1 of the present invention (when R is hydrogen). η ⁵ -NC ₄ Me ₄ ) is obtained (see Figure 3).

In steps 1-4, the trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) [Ru(CHT) (η ⁵ -NC ₄ Me ₄ ) ] The amount of lithium aluminum tri(t-butoxy) hydride (LiAl(O ^t Bu) ₃ H) used for (OTf) is 1:1.1 to 1:1.2 (molar ratio).

The ether solvent may be any ether solvent known in the art, and is preferably THF. Additionally, other solvents with similar polarity may be used as needed.

Reaction of the trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) [Ru(CHT) (η ⁵ -NC ₄ Me ₄ )] (OTf) The amount of ether solvent added to the container is the reactant trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) [Ru(CHT) (η ⁵ -NC ₄ Me ₄ )] (OTf) may be 10 to 40 times the amount used (weight ratio). Preferably, it may be 20 to 30 times (weight ratio), but may also be determined depending on the amount of the reactant used.

The amount of ether solvent added to the reaction vessel of lithium aluminum tri(t-butoxy) hydride (LiAl(O ^t Bu) ₃ H) is the reactant, lithium aluminum tri(t-butoxy) hydride (LiAl(O ^t Bu) ₃ H). It may be 10 to 30 times the amount used (weight ratio). Preferably, it may be 10 to 25 times, but may also be determined depending on the amount of the reactant used.

The time taken to transfer the reactants from one reaction vessel to another reaction vessel may be about 10 minutes to 1 hour, preferably 20 minutes to 40 minutes, but may be determined depending on the amount of reactants used. However, the transfer must be determined within a time period in which only a mild exothermic reaction is observed.

The stirring time at room temperature is 1 to 5 hours, preferably 1 to 3 hours, but the stirring time may be determined depending on the amount of reactant used.

The first non-polar solvent is a common non-polar solvent, and is preferably a nucleic acid (hexane). The second non-polar solvent is a solvent with lower polarity than the first non-polar solvent, and is preferably pantane.

The following production method, which is another specific example of the production method of the present invention including steps 2-1 to 2-4 of (i) to (iv), is when R in the ruthenium organometallic compound of Formula 1 is a methyl group, that is, This is a specific manufacturing method of Ru(η ⁵ - ^Me CHeptD)(η ⁵ -NC ₄ Me ₄ ).

(Step 2-1)

(Step 2-2)

(Step 2-3)

delete

(Steps 2-4)

In steps 2-1 to 2-4, '1,3,5-cycloheptatriene (CHT)', the reactant of step 1-1 of the production method of an embodiment of the present invention, is used. It is the same as steps 1-1 to 1-4 except that it is changed to '7-methyl-1,3,5-cycloheptatriene ( ^Me CHT)'. However, there may be differences in purification methods due to differences in compounds, such as products.

As described above, the ruthenium organometallic compound represented by Chemical Formula 1 of the present invention, manufactured by the production method of one embodiment and another embodiment of the present invention, is thermally stable and has good volatility as a solid or liquid at room temperature, so it can be used in chemical vapors. It is a compound suitable for the ruthenium thin film process using vapor deposition or atomic layer deposition (see Figure 13).

The present invention can be better understood by the following examples, which are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.

In addition, the present invention is not limited to the following examples, and various modifications are possible without departing from the gist of the present invention as claimed in the claims.

Example 1: Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ )Manufacture of

Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) when R in Formula 1 of the present invention is hydrogen is obtained from steps 1-1 to 1-4 below.

<Step 1-1: Dichloro(cycloheptatriene)ruthenium(II)-dimer ([Ru(CHT)Cl ₂ ] ₂ Manufacturing>

RuCl3.xH2O (37% Ru, 250.0g, 0.915 mol) and cycloheptatriene (222g, 250mL, 2.41 mol) were filled in a flask, dissolved in ethanol (2.5L), and the solution was bubbled for 20 minutes using N ₂ gas. do. The mixture is heated to reflux for 72 hours. After cooling to room temperature, stop stirring to allow the undissolved solid to settle to the bottom of the flask. Remove part of the solution using a cannula. Fill the flask with the solid with diethyl ether (500 mL) and stir for several minutes, then stop stirring to allow the undissolved solid to settle again, and remove the solution again using the cannula. After filling the flask with diethyl ether (500mL), filter the solution through a glass filter and wash the remaining solid with diethyl ether until the washing solution becomes completely colorless. The obtained solid was completely dried under vacuum to obtain the title compound [Ru(CHT)Cl ₂ ] ₂ (235 g, 98%) as a brown solid.

¹ H-NMR (CF ₃ COOD): 6.62 (2H _a , mult), 5.21 (2H _b , mult), 4.30 (2H _c , mult), 3.17 (1H _d , mult), 1.00 (1H _e , mult).

The NMR data of the title compound obtained from step 1-1 is shown in Figure 1.

<Step 1-2: [Ru(CHT)(OTf) ₂ ] ₂ Manufacturing>

In the glove box, fill the flask with [Ru(CHT)Cl ₂ ] ₂ (243.3 g, 0.461 mol) and Ag(OTf) (458.2 g, 1.89 mol), block it with a septum, and remove the flask from the glove box. Dichloromethane (4L) was dissolved in a flask under N ₂ gas and stirred at room temperature for 24 hours (at this time, a gray solid was formed in the orange/brown solution). After finishing stirring, the reaction mixture is filtered through a celite filter, and the celite is washed with DCM (Dichloromethane) until the filtrate becomes colorless. Volatile substances are removed through reduced pressure distillation. The solid thus obtained was completely dried under vacuum to obtain the title compound [Ru(CHT)(OTf) ₂ ] ₂ (310 g, 70%) as a dark brown solid.

¹ H-NMR analysis confirmed that the starting material was consumed and converted to another compound. No additional purification process is performed.

<Step 1-3: [Ru(CHT)(η ⁵ -NC ₄ Me ₄ )]Manufacture of (OTf)>

In the glove box, add [Ru(CHT)(OTf) ₂ ] ₂ (50.0 g, 50.9 mmol) to the flask, then remove the flask from the glove box and dissolve it in dichloromethane (800 mL) under N ₂ gas (Container 1). . Inside the glove box, fill another flask with 2,3,4,5-tetramethylpyrolle (12.9 g, 104.3 mmol), remove it from the glove box, and dissolve it in DCM (150 mL) (container 2). The solution in container 2 was transferred to container 1 over 15 minutes using a cannula (at this time, a mild exothermic reaction was observed), and then the mixture of containers 1 and 2 was stirred in a dark room at room temperature for 24 hours. Remove volatile substances using vacuum and proceed until approximately 100 mL of solution remains. Using ethyl acetate as an eluent, impurities (R _f =0.7, 0.9) are removed through a short neutral alumina column. The product remaining in the alumina is eluted using DCM (Dichloromethane)/MeCN (Acetonitrile) (v/v 2:1) solution. The volatiles were removed under vacuum to give a sticky brown solid. The obtained solid was dissolved in DCM and then dried again to obtain the title compound [Ru(CHT)(η ⁵ -NC ₄ Me ₄ )](OTf) (38g, 80%) as a yellow-brown solid. ¹ It was confirmed that it was the desired product through H-NMR analysis.

^1H -NMR (CDCl ₃ ): 6.55 (2H _a , mult), 5.35 (2H _b , mult), 3.59 (2H _c , mult), 3.02 (1H _d , mult), 2.10 (6H _e , s), 1.95 (6H _f , s), 1.02 (1H _g , mult).

NMR data for the title compound obtained from <Step 1-3> is shown in Figure 2.

<Step 1-4: Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ )Manufacture>

[Ru(CHT)(η ⁵ -NC ₄ Me ₄ )](OTf) in the glove box (30.0 g, 64.6 mmol) was placed in a flask, taken out of the glove box, and dissolved in THF (800 mL) under N ₂ gas (container 1). LiAl(O ^tBu ) ₃ H (18.1 g, 71.1 mmol) was also added to the flask in the glove box and then dissolved in THF (400 mL) under N ₂ gas (container 2). The solution in vessel 2 was transferred to vessel 1 via a cannula over 30 minutes (at this time, a mild exothermic reaction was observed), and the mixture in vessels 1 and 2 was stirred at room temperature for 2 hours. After finishing stirring, volatile substances (solvent) are removed through vacuum. The remaining red solid is extracted using hot hexane and filtered through a short alumina layer (1 to 2 cm). Wash the alumina layer with hexane until the washing solution becomes colorless. The filtrate is concentrated via vacuum. The obtained yellow solid is dissolved using a minimum amount of pentane and recrystallized at -40 ^o C. The obtained crystals are filtered using a filter and washed with pentane cooled to -70 ^o C. The obtained solid was completely dried in vacuum to obtain the title compound Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) (4g, 20%).

¹ Through H-NMR analysis, it was confirmed that the yellow crystal was the desired product.

^OneH-NMR (CDCl₃): 5.29 (1H_a, mult), 4.36 (2H_b, mult), 3.35 (2H_c, mult), 2.01 (6H_d, s), 1.97 (6H_e, s), 1.72 (2H_f, mult), 1.06 (2H_g, mult).

NMR data for the obtained title compound, the compound of formula 1 of the present invention (when R is hydrogen), is shown in FIG. 3.

Example 2: Ru(η ⁵ - ^Me CHeptD)(η ⁵ -NC ₄ Me ₄ )Manufacture of

Ru(η ^{5 -Me} CHeptD)(η ⁵ -NC ₄ Me ₄ ), in which R in Formula 1 of the present invention is a methyl group, is obtained from steps 2-1 to 2-4 below.

<Step 2-1: [Ru( ^Me CHT)Cl ₂ ] ₂ Manufacturing>

RuCl3.xH2O (37% Ru, 47.0g, 172 mmol) and 7-methylcycloheptatriene (67.6g, 637 mmol) were filled in a flask, dissolved in ethanol (500mL), and the solution was bubbled for 20 minutes using N ₂ gas. do. The mixture was heated to reflux for 72 hours and cooled to room temperature, then stirring was stopped to allow the undissolved solid to settle to the bottom of the flask. Remove part of the solution using a cannula. Fill the flask with the solid with diethyl ether (100 mL) and stir for several minutes, then stop stirring to allow the undissolved solid to settle again. Remove the solution again using the cannula. After filling the flask with diethyl ether (100mL), filter the solution through a glass filter and wash the remaining solid with diethyl ether until the washing solution becomes completely colorless. The obtained solid was completely dried through vacuum to obtain the title compound [Ru( ^Me CHT)Cl ₂ ] ₂ (35.0 g, 73%) as a yellow-brown solid.

¹ Through H-NMR analysis, it was confirmed that the compound was a mixture of isomers.

NMR of the mixture: ¹ H-NMR (CDCl ₃ ): 6.51 (CH, s), 6.37 (CH, mult), 5.13 (CH, s), 5.06 (CH, mult), 4.90 (CH, mult), 4.15 (CH, bs), 3.87 (CH , s), 3.05 (CH ₂ , mult), 2.83 (CH ₂ , mult), 2.51 (CH ₃ , s), 1.96 (CH ₃ , s), 1.49 (CH ₃ , d), 1.31 (CH ₂ , mult) ), 0.98 (CH ₂ , mult).

<Step 2-2: : [Ru( ^Me CHT)(OTf) ₂ ] ₂ Manufacturing>

In the glove box, [Ru( ^Me CHT)Cl ₂ ] ₂ (30.8 g, 55.4 mmol) and Ag(OTf) (58.3 g, 227 mmol) were filled into the flask, blocked with a septum, and the flask was taken out of the glove box. Dissolve Dichloromethane (600mL) in the flask under N ₂ gas and stir at room temperature for 24 hours. At this point, a gray solid is formed in the orange/brown solution. After finishing stirring, the reaction mixture is filtered through a celite filter, and the celite is washed with DCM (Dichloromethane) until the filtrate becomes colorless, and the filtrate is collected. The collected filtrate was subjected to reduced pressure distillation to remove volatile substances, and the obtained solid was completely dried in vacuum to obtain the title compound [Ru( ^Me CHT)(OTf) ₂ ] ₂ (53.5 g, 96%) as a dark brown solid. . It was used in the next step, steps 2-3, without any additional purification process.

<Step 2-3: Ru( ^Me CHT)(η ⁵ -NC ₄ Me ₄ )]Manufacture of (OTf)>

In the glove box, add [Ru( ^Me CHT)(OTf) ₂ ] ₂ (53.5 g, 52.9 mmol) to the flask, then remove the flask from the glove box and add DCM (dichloromethane) (500 mL) under N ₂ gas to dissolve it. (Container 1). Inside the glove box, fill another flask with 2,3,4,5-tetramethylpyrrole (13.4 g, 108 mmol), remove it from the glove box, and dissolve it in DCM (150 mL) (container 2). The solution in container 2 was transferred to container 1 over 15 minutes using a cannula (a weak exothermic reaction was observed), and then the mixture of containers 1 and 2 was stirred in a dark room at room temperature for 24 hours. Remove volatile substances (solvent) using vacuum and proceed until approximately 100 mL of solution remains. Using ethyl acetate as an eluent, impurities are removed through a short neutral alumina column, and the product remaining in the alumina is eluted using MeCN (acetonitrile). The volatile material (solvent) was removed under vacuum to obtain a sticky brown solid. The obtained solid was dissolved in DCM and dried again to obtain the title compound [Ru( ^Me CHT)(η ⁵ -NC ₄ Me ₄ )](OTf) (30.6g, 60%) as a reddish-brown solid. did.

Through H-NMR analysis, it was confirmed that the obtained compound was a mixture of isomers. The mixture of the isomers was purified through silica gel column chromatography (DCM/MeCN = 2:1 and MeCN = 100%) to obtain two isomer compounds (see FIGS. 7 and 8).

<Step 2-4: Ru(η ⁵ - ^Me CHeptD)(η ⁵ -NC ₄ Me ₄ )Manufacture>

[Ru( ^Me CHT)(η ⁵ -NC ₄ Me ₄ )](OTf) in the glove box (20.0 g, 41.8 mmol) was placed in a flask, taken out of the glove box, and dissolved in THF (450 mL) under N2 gas (container 1). LiAl(O ^tBu ) ₃ H (11.7 g, 46.0 mmol) was also added to the flask in the glove box and then dissolved in THF (150 mL) under N ₂ gas (container 2). The solution in vessel 2 was transferred to vessel 1 via cannula over 30 minutes (observation of a mild exothermic reaction), and the mixture in vessels 1 and 2 was stirred at room temperature for 2 hours. After finishing stirring, volatile substances (solvent) are removed through vacuum. The remaining red oily solid is extracted using hexane and filtered through a short alumina layer (1 to 2 cm). Wash the alumina layer with hexane until the washing solution becomes colorless. The red liquid produced by concentrating the filtrate through vacuum was transferred to a distillation device and distilled in high vacuum (p<0.001 torr) to produce the title compound Ru(η ⁵ - ^Me CHeptD)(η 5 -NC 4 Me 4) (η ⁵ -NC ₄ Me ₄ ) as a yellow liquid. 5.8g, 42%) was obtained.

¹ H-NMR analysis confirmed that the product was an isomer mixture, and the bp of this mixture was 80°C (0.001 torr).

The isomer mixture was purified through silica gel column chromatography (hexane/ethyl acetate = 4:1) to obtain two isomer compounds (see Figures 9 and 10).

Example 3: Thermogravimetric analysis test of ruthenium compounds

Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), a ruthenium organometallic compound represented by the formula 1 (R=H) of the invention in Example 1, and Formula 1 (R) of the invention of Example 2 =Me), a ruthenium organometallic compound, Ru(η ⁵ - ^Me CHeptD)(η ⁵ -NC ₄ Me ₄ ), was analyzed using TGA (thermogravimetric analysis). In the TGA test, the test specimen was analyzed while raising the temperature to 500°C at a rate of 10°C/min, and the TGA graph and results are shown in Figures 4 and 11, respectively, and Table 1 below.

Compound name Compound of Example 1
(of the present invention Formula 1
When R is hydrogen) Compound of Example 2
(of the present invention Formula 1
When R is a methyl group) Previously known compounds
(Rudense) T _1/2 ℃ 248.9℃ 248.9℃ 219.8℃ Residual Mass (%) 0.1% 0% 12.2%

From Table 1 and the TGA graphs of FIGS. 4 and 11, the newly synthesized ruthenium organometallic compound of Formula 1 in Examples 1 and 2 of the present invention has a temperature (T _1/2 ℃) at which its weight is reduced by half in FIG. 14. It shows a much higher temperature than Rudense, a compound known conventionally as a precursor for ruthenium thin films (see FIGS. 4, 11, and 14).

In addition, the newly synthesized ruthenium organometallic compounds of Chemical Formula 1 of Examples 1 and 2 of the present invention appear to have a Residual Mass value significantly lower than that of the Comparative Example, so the ruthenium organometallic compounds of Chemical Formulas 1 and 2 of the present invention are those of the Comparative Example. It can be seen that it is a ruthenium compound with improved thermal stability compared to Rudense, a ruthenium compound.

Due to this high thermal stability, the ruthenium organometallic compound of Chemical Formula 1 of the present invention has the advantage of being able to stably form a ruthenium film not only at low temperatures but also in high temperature deposition processes.

Example 4: Differential scanning calorimetry analysis experiment of ruthenium compounds

Examples 1 and 2 of the present invention Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), which is a ruthenium organometallic compound represented by Chemical Formula 1, and Ru(η ⁵ - ^Me CHeptD)(η ⁵ -NC ₄ ) Me ₄ ) was measured by differential scanning calorimetry (DSC) at high and low temperatures, respectively. analyzed.

In the DSC test, Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ), which is the ruthenium organometallic compound of Formula 1 of the present invention in Examples 1 and 2, and Ru(η ^{5 -Me} CHeptD)(η ⁵ -NC ₄ Me ₄ ) was analyzed while raising the temperature to 400°C at a rate of 10°C/min.

The results are shown in Figures 5 and 12, and Table 2 below.

Compound name Example 1 Example 2 Previously known compounds
(Ludens) T _{(dec, start)} ℃ 250℃ 251℃ 170℃ T _{(dec max)} ℃ 340℃ 341℃ 292℃

Table 2 shows that the thermal decomposition behavior of the ruthenium organometallic compound of the present invention represented by Chemical Formula 1 of Examples 1 and 2 starts at a higher temperature than that of Rudense, a compound of Comparative Example. The high thermal decomposition temperature of the ruthenium organometallic compound represented by Formula 1 of Examples 1 and 2 of the present invention is such that the ruthenium organometallic compound represented by Formula 1 of the present invention has improved thermal stability at high temperatures compared to Rudense, a comparative example compound. It can be seen that it is a compound.

As described above, the ruthenium organometallic compound of Formula 1 of the present invention in Examples 1 and 2 has the advantage of thermal stability for forming a ruthenium thin film even in a high temperature process.

Example 5: Thin film formation process of ruthenium organometallic compound of Example 1 of the present invention

<Tabernacle test>

Using the ruthenium organometallic compound of the present invention as a raw material, a ruthenium thin film was formed using a CVD device. Film formation conditions, processes, and results are as follows.

go. Tabernacle formation conditions

- Substrate: SiO2 substrate

- Substrate temperature: 450℃

- Sample temperature (vaporization temperature): 120℃

- Chamber pressure: 5 Torr

- Reactive gas: ammonia (NH ₃ )

- Sample and reactive gas injection time: 60 min

- Reactive gas injection amount: ammonia 500 sccm

- Sheet resistance: 33763 Ω/□

me. Film formation process and results

A ruthenium thin film was formed by injecting the ruthenium organometallic compound of the present invention and the reactive gas ammonia for a certain period of time under the film formation conditions described above, and the thin film deposition rate of the film was constant at 0.5 Å/min. This confirms that the novel ruthenium organometallic compound of the present invention undergoes uniform CVD growth. In addition, the film thickness of the ruthenium thin film was measured using a transmission electron microscope (TEM), and the film thickness of the ruthenium thin film was 30 Å (see FIG. 13).

The ruthenium thin film manufactured using the compound represented by Formula 1 of the present invention can be used in the production of semiconductors, etc.

Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. possible.

Claims (7)

A ruthenium organometallic compound, characterized in that represented by the following formula (1):
[Formula 1]

In Formula 1, R is hydrogen; Or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. In claim 1,
Ruthenium organometallic compound, characterized in that R is a methyl group A method for producing a compound in the formula (1) wherein R is hydrogen, comprising steps 1-1 to 1-4 of (a) to (d) below:
[Formula 1]

(a) Step 1-1 of obtaining dichloro(cycloheptatriene)ruthenium(II)-dimer from ruthenium chloride hydrate and 1,3,5-cycloheptatriene;
(b) Ditrifluoromethanesulfonate (cycloheptatriene) from dichloro(cycloheptatriene)ruthenium(II)-dimer and silver trifluoromethanesulfonate (Ag(OTf)) in step 1-1. Step 1-2 of preparing ruthenium (II)-dimer;
(c) Trifluoromethane sulfonate (cycloheptatriene) from ditrifluoromethanesulfonate (cycloheptatriene) ruthenium (II)-dimer and 2,3,4,5-tetramethylpyrrole in step 1-2 ) (2,3,4,5-tetramethylpyrrole) steps 1-3 for producing ruthenium (II); and
(d) trifluoromethanesulfonate (cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) and lithium aluminum tri (t-butoxy) hydride (LiAl) of steps 1-3 Steps 1-4 to obtain Ru(η ⁵ -CHeptD)(η ⁵ -NC ₄ Me ₄ ) from (O ^t Bu) ₃ H);
Ru(η ⁵ -CHeptD) and (η ⁵ -NC ₄ Me ₄ ) in steps 1-4 are Ru(η ⁵ -cycloheptadiene) and (η ⁵ -2,3,4,5-tetramethylpyrrole, respectively. )am. A method for producing a compound of the following formula (1) where R is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, comprising steps 2-1 to 2-4 of (i) to (iv) below: method
[Formula 1]

(i) Step 2-1 of obtaining dichloro(R-cycloheptatriene)ruthenium(II)-dimer from ruthenium chloride hydrate and R-1,3,5-cycloheptatriene;
(ii) Ditrifluoromethanesulfonate (R-cycloheptatriene) from dichloro(R-cycloheptatriene)ruthenium(II)-dimer and silver trifluoromethanesulfonate (Ag(OTf)) in step 2-1. Step 2-2 of producing heptatriene) ruthenium (II)-dimer;
(iii) Trifluoromethane sulfonate (R- Step 2-3 for producing cycloheptatriene)(2,3,4,5-tetramethylpyrrole)ruthenium(II); and
(iv) Trifluoromethanesulfonate (R-cycloheptatriene) (2,3,4,5-tetramethylpyrrole) ruthenium (II) and lithium aluminum tri(t-butoxy) hydride in steps 2-3 above. Steps 2-4 to obtain Ru(η ^{5 -R} CHeptD)(η ⁵ -NC ₄ Me ₄ ) from (LiAl(O ^t Bu) ₃ H);
Ru(η ^{5 -R} CHeptD)(η ⁵ -NC ₄ Me ₄ ) in step 2-4 is Ru(η ⁵ -R-cycloheptadiene)(η ⁵ -2,3,4,5-tetramethylpyrrole )ego,
R in steps 2-1 to 2-4 is a straight or branched alkyl group having 1 to 4 carbon atoms. A method of forming a ruthenium thin film using the ruthenium organometallic compound of claim 1 or 2, wherein the thin film forming process is chemical vapor deposition (CVD) or atomic layer deposition (ALD).


delete delete