KR20100061183A - Organometallic precursors for deposition of metallic cobalt and cobalt containing ceramic films, and deposition process of the thin films - Google Patents

Abstract

PURPOSE: An organo metallic precursor for depositing a ceramic thin film and a manufacturing method of the thin film using thereof are provided to secure the high thermal stability and the high vapor pressure for manufacturing a semiconductor device. CONSTITUTION: An organo metallic precursor for depositing a ceramic thin film or a metal thin plate containing cobalt is marked with chemical formula 1. A manufacturing method of the organo metallic precursor comprises the following: adding 1,4-diaza-2,3-butadien system compound to a cyclopentadienyl cobalt die carbonyl compound under the presence of a non-polar solvent or a weak-polarity solvent; and operating a reflux reaction before the decompression and the distillation of the mixture.

Description

Organometallic precursors for deposition of metallic cobalt and cobalt containing ceramic films, and deposition process of the thin films}

The present invention relates to an organic metal precursor for depositing a metal thin film containing cobalt such as metal cobalt or cobalt silicide or a ceramic thin film containing cobalt such as cobalt oxide, which is applied to a semiconductor device. The present invention relates to an organic metal precursor compound for depositing a metal thin film or ceramic thin film containing cobalt used in Atomic Layer Deposition (ALD) or Metal Organic Chemical Vapor Deposition (MOCVD), and a method for manufacturing a thin film using the same.

Currently, when forming a contact plug in a metal oxide semiconductor device (MOS device), a low-resistance titanium silicide film (TiSi ₂ ) is used as an ohmic layer. However, the titanium silicide layer has a disadvantage in that the resistance increases when the contact hole size decreases or when high temperature heat is applied. In particular, the titanium silicide layer has a titanium-p-type junction (p type) in a p-type MOS device (p-type PMOS) under 100 nm process. Titanium boride (TiB ₂ ) is formed due to high reactivity with boron (B) in the juction region, which causes a problem of greatly increasing contact resistance.

Accordingly, metal cobalt has very low reactivity with boron compared to titanium, so that there is no problem of increasing contact resistance due to cobalt boride (CoB) formation, and lower resistivity than titanium silicide film when forming cobalt silicide film (10 ~ 18μΩ · cm) excellent thermal stability has been studied to use cobalt silicide as an ohmic contact layer in the next-generation semiconductor process. In particular, as the degree of integration of semiconductor devices increases and the structure thereof becomes more complicated, in order to deposit a thin film having excellent step coverage on a structure having a high aspect ratio, the organic organic chemical vapor deposition method (Metal Organic Chemical) Cobalt silicide thin films must be deposited using Vapor Deposition (MOCVD) or Atomic Layer Deposition (ALD).

Such cobalt oxide thin films are being studied in a wide range of applications such as magnetic detectors, moisture and oxygen sensors, and especially CoO and Co ₃ O ₄ thin films are buffer films of perovskite layers such as high-Tc superconductors. It acts as a (buffer layer) and is of great interest.

On the other hand, one of the biggest problems in applying copper metal to wiring in the next-generation semiconductor wiring process is that the adhesion between the copper thin film of the wiring layer and the diffusion barrier is poor. In particular, when a CMP (Chemical Mechanical Polishing) process for forming vias or the like occurs, a problem arises that delamination of copper wiring occurs due to low adhesion between the copper thin film and the diffusion barrier. This problem can be solved by using a metal cobalt thin film as an adhesive layer to improve adhesion between the copper thin film and the diffusion barrier, and in order to use the metal cobalt thin film as an adhesive layer, a MOCVD or ALD process is also used. A uniform thin film should be deposited.

Conventional cobalt precursors used to deposit thin films such as metal cobalt, cobalt silicide, and cobalt oxide using MOCVD or ALD processes are typically Co ₂ (CO) ₈ (dicobalt octacarbonyl) and Cp ₂ Co (biscyclopentadienylcobalt). , Co (CO) ₃ (NO) (cobalt tricarbonyl nitrosyl), CpCo (CO) ₂ (cabalt dicarbonyl cyclopentadienyl) and the like are known.

However, although Co (CO) ₃ (NO) and CpCo (CO) ₂ compounds are liquid and have a high vapor pressure, they may cause a lot of difficulties in the process due to thermal instability such as pyrolysis at room temperature. There was this. In particular, the CpCo (CO) ₂ compound has better thermal stability than Co (CO) ₃ (NO), but it is known that decomposition starts at 140 ° C., causing contamination of carbon and oxygen in the final thin film.

In addition, the Co ₂ (CO) ₈ and Cp ₂ Co compounds are not only solid at room temperature but also relatively low in vapor pressure, and in particular, Co ₂ (CO) ₈ is known to occur to a certain degree of decomposition reaction at room temperature. It is reported that decomposed above the ℃, the step coverage of the final thin film due to undesired side reactions in the gas phase such as Co ₂ (CO) ₇ and Co ₄ (CO) ₁₁ and severe contamination of carbon and oxygen in the thin film.

As described above, cobalt precursors are known to have thermal difficulties due to thermal instability such as pyrolysis at room temperature. Thus, cobalt-containing thin films or metal oxides or metal nitrides containing cobalt by atomic layer deposition at a wide range of process temperatures are present. There is a need for a precursor capable of depositing the same ceramic thin film.

Accordingly, the present invention is to solve the problems of the conventional cobalt precursors mentioned above, and is an organic metal precursor for depositing a metal thin film or ceramic thin film containing cobalt that is thermally stable, increases volatility, and exists in a liquid state at room temperature. The purpose is to provide a compound.

In addition, the present invention is to provide a method for producing a metal cobalt, cobalt silicide, cobalt oxide thin film by the organic metal chemical vapor deposition method or atomic layer deposition method using the above-described organometallic precursor.

According to an aspect of the present invention,

Organic metal precursor for cobalt metal thin film or cobalt-containing ceramic thin film, characterized in that the organometallic precursor compound used for depositing the cobalt-containing metal thin film and the cobalt-containing ceramic thin film is an organic metal precursor compound It provides a precursor compound.

<Formula 1>

In Formula 1 R ¹ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² , and — (CH ₂ ) _n OR ¹³ . alkoxy group represented _{(alkoxyalkyl), - (CH 2} ) are selected from among _n NR ¹⁴ R ¹⁵ dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, the present invention provides a method for producing a metal cobalt, cobalt silicide, cobalt oxide thin film using an organometallic chemical vapor deposition method or an atomic layer deposition method using the above-described organometallic precursor.

As described above, it was confirmed experimentally that the organometallic precursor compound of the present invention is suitable for depositing cobalt-containing metal thin films such as cobalt metal and cobalt silicide and ceramic thin films containing cobalt oxide and cobalt nitride. In particular, the precursor compounds developed in the present invention have a high vapor pressure with high thermal stability that does not deteriorate even under continuous heating, so that metal cobalt, cobalt silicide, etc. using organic metal chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) Cobalt-containing metal thin film and cobalt oxide, cobalt nitride and the like can be useful in the semiconductor manufacturing process of depositing a ceramic thin film containing cobalt.

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

In the present invention, an organic metal precursor compound for depositing a metal thin film or a ceramic thin film containing cobalt such as metal cobalt, cobalt silicide (Cobalt silicide, CoSi and CoSi ₂ ) and cobalt oxide (Cobalt oxide) is defined by the following formula (1) Organometallic compound.

In Formula 1 R ¹ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² , and — (CH ₂ ) _n OR ¹³ . alkoxy group represented _{(alkoxyalkyl), - (CH 2} ) are selected from among _n NR ¹⁴ R ¹⁵ dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

The organometallic precursor compound of the present invention represented by Chemical Formula 1 may improve thermal stability by introducing a cyclopentadienyl-based ligand capable of strongly binding to metal cobalt ions. In particular, by incorporating an electron donation substituent including an alkyl group capable of donating electrons with one hydrogen of a cyclopentadienyl ligand, the binding between metal cobalt ions and the ligand is enhanced.

In addition, 1,4-diaza-1,3-butadiene (1,4-diaza-1,3-butadiene; R ⁶ NCR ⁸ CR ⁹ NR ⁷ ) -based ligands introduced as neutral ligands are chelating. As a ligand, it not only binds strongly to metal ions but also has a low energy level π ^* orbital in the ligand itself, which can stabilize metal ions such as cobalt having a low oxidation number. It is the ideal precursor for chemical vapor deposition or atomic layer deposition that can solve the problems of the existing cobalt precursor.

In addition, R ² to R ⁵ are each hydrogen (H) in order to have high volatility in order to easily apply to chemical vapor deposition or atomic layer deposition without contamination of impurities in the final thin film among the organometallic precursor compounds represented by Formula 1 The organometallic precursor compound represented by the following formula (2) is preferred.

In Formula 2, R ¹ and R ⁶ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, or a trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² . ), An alkoxyalkyl group represented by-(CH ₂ ) _n OR ^13, and a dialkylaminoalkyl group represented by-(CH ₂ ) _n NR ¹⁴ R ¹⁵ . N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, among the organometallic precursor compounds of Formula 2, an organometallic precursor compound represented by the following Formula 3 wherein R ¹ is an ethyl group is preferable.

R ⁶ to R ⁹ in Formula 3 may each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, a trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² , It is selected from the alkoxyalkyl group represented by (CH ₂ ) _n OR ^13, and the dialkylaminoalkyl group represented by-(CH ₂ ) _n NR ¹⁴ R ¹⁵ . N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, in the compound represented by Chemical Formula 3, R ⁶ and R ⁷ are both isopropyl groups, and R ⁸ and R ⁹ are hydrogen (H). Or as an organometallic precursor compound used for depositing a ceramic thin film.

In addition, among the organometallic precursor compounds of Formula 2, an organometallic compound represented by the following Formula 5 wherein R ¹ is an isopropyl group is preferably used.

In Formula 5, R ⁶ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ^12, and a trialkylsilylalkyl,-( CH ₂₎ alkoxyalkyl group (alkoxyalkyl) represented by _n OR ^13, - are selected from ^{_{(CH 2) n NR 14 R}} 15 dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, in the compound represented by Chemical Formula 5, R ⁶ and R ⁷ are both isopropyl groups, and R ⁸ and R ⁹ are all hydrogen or organic compounds represented by the following Chemical Formula 6, wherein the cobalt-containing metal thin film or ceramic thin film It is more preferable as a precursor compound in the organic metal used for depositing.

As described above, the organometallic precursor compound for chemical vapor deposition or atomic layer deposition represented by Chemical Formula 1 may be prepared by various methods, but in the present invention, as shown in Scheme 1, a nonpolar solvent or a solvent having a weak polarity is represented. 1,4-diaza-1,3-butadiene (R ⁶ NCR ⁸ ) in a cyclopentadienyl cobalt dicarbonyl (R ¹ R ² R ³ R ⁴ C ⁵ HC ₅ Co (CO) ₂ ) compound solution The CR ⁹ NR ⁷ ) -based ligand can be easily obtained by adding a ligand at room temperature, followed by reflux stirring, and distillation under reduced pressure.

In this case, benzene, hexane, toluene, ethylcyclohexane, and the like may be used as a solvent. In order to suppress the decomposition reaction due to moisture or oxygen during the reaction, nitrogen ( It is preferable to proceed with the reaction under N ₂ ) or argon (Ar) stream.

Scheme 1

R ¹ to R ⁹ in Scheme 1 are as defined in Chemical Formula 1.

The compound defined by Chemical Formula 1 synthesized by the present invention is an organic cobalt metal compound having excellent thermal and chemical stability, present as a liquid at room temperature, and having high volatility, and is used as a precursor of an organic metal chemical vapor deposition method or an atomic layer deposition method. Cobalt, cobalt silicide, cobalt oxide and cobalt nitride thin film can be usefully used.

When the thin film is deposited on the substrate by using the organometallic precursor compound defined by Chemical Formula 1 according to the present invention, the deposition temperature may be 150 ° C to 700 ° C. In this case, in order to vaporize the organometallic precursor compound, bubbling with argon (Ar) or nitrogen (N ₂ ) gas, using thermal energy or plasma, or applying a bias on the substrate. In addition, the delivery method for supplying the organometallic precursor compound according to the present invention to a process may include a bubbling method, a vapor phase mass flow controller (MFC), a direct liquid injection (DLI), or a precursor compound. Various feeding methods may be applied, including a liquid transfer method for dissolving and dissolving it in an organic solvent.

One or more mixtures of argon (Ar), nitrogen (N ₂ ), helium (He), or hydrogen (H ₂ ) may be used as a carrier gas or a diluent gas for supplying the precursor to the process. In addition, in order to deposit cobalt oxide thin films by atomic layer deposition (ALD) and chemical vapor deposition (CVD), steam (H ₂ O), oxygen (O ₂ ) and ozone (O ₃ ) are used as reaction gases. ) And ammonia (NH ₃ ) or hydrazine (N ₂ H ₄ ) as a reaction gas to deposit cobalt nitride thin films by atomic layer deposition (ALD) and chemical vapor deposition (CVD). ) Can be used. In addition, hydrogen (H ₂ ) or silane is used as a reaction gas to deposit a thin metal film containing cobalt such as metal cobalt and cobalt silicide by atomic layer deposition (ALD) and chemical vapor deposition (CVD). (Silane) type compounds can be used.

Hereinafter, the organic metal precursor compound for depositing a cobalt-containing metal thin film or ceramic thin film according to the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention. This is not limited to the following examples.

<Example 1>

Preparation of ^Et CpCo ( ⁱ Pr ₂ -DAD)

20 g (0.1 mol) of ^Et CpCo (CO) ₂ is diluted in 200 mL of ethylcyclohexane, and the solution is diluted with N, N' -diisopropyl-1,4-diaza-1,3-butadiene ( 14.02g (0.1mol) of N, N'-diisopropyl-1,4-diaza-1,3-butadiene, ⁱ Pr ₂ -DAD) was added at room temperature, followed by stirring the mixed solution for 4 days using a reflux condenser. During reflux reaction. After completion of the reaction, the solvent and volatile side reactions were removed under reduced pressure, extracted with normal hexane (n-hexane, C ₆ H ₁₄ ), and filtered through a glass filter to remove the solvent and volatile side reactions under reduced pressure. You get this high dark reddish brown liquid. This liquid was distilled under reduced pressure to obtain 18.7 g (yield: 63.97%) of ^Et CpCo ( ⁱ Pr ₂ -DAD) as a highly viscous reddish brown liquid compound.

Elemental Analysis: cacld. for C ₁₅ H ₂₅ N ₂ Co: C, 61.63; H, 8.62; N, 9.58. found: C, 61.67; H, 8.59; N, 9.56.

Boiling Point (b.p): 84 ° C at 0.19torr.

Density: 1.299g / ml at 25 ℃

¹ H-NMR (C ₆ D ₆ ): δ 1.195 ([C H ₃ CH ₂ C ₅ H ₄ ] -Co, t, 3H),

δ 1.504, 1.521 ([(C H ₃ ) ₂ CH-N = CHCH = N-CH (C H ₃ ) ₂ ] -Co, d, 12H),

δ 2.516, 2.534 ([CH ₃ C H ₂ C ₅ H ₄ ] -Co, q, 2H),

δ 4.326, 4.510 ([CH ₃ CH ₂ C ₅ H ₄ ] -Co, br, br, 2H, 2H),

δ 5.068 ([(CH ₃ ) ₂ C H —N═CHCH = NC H (CH ₃ ) ₂ ] —Co, sept, 2H),

δ 6.966 ([(CH ₃ ) ₂ CH—N═C H C H = N—CH (CH ₃ ) ₂ ] —Co, s, 2H).

¹³ C-NMR (C ₆ D ₆ ): δ 16.737 ([ C H ₃ CH ₂ C ₅ H ₄ ] -Co),

δ 21.423 ([CH ₃ C H ₂ C ₅ H ₄ ] -Co),

δ 24.234 ([[( C H ₃ ) ₂ CH-N = CHCH = N-CH ( C H ₃ ) ₂ ] -Co),

δ 63.418 ([(CH ₃ ) ₂ C H-N = CHCH = N- C H (CH ₃ ) ₂ ] -Co),

δ 74.132 ([(CH ₃ ) ₂ CH-N = C H C H = N-CH (CH ₃ ) ₂ ] -Co),

δ 98.769, 132.802 ([CH ₃ CH ₂ C ₅ H ₄ ] -Co),

<Example 2>

Preparation of ^iPr CpCo ( ⁱ Pr ₂ -DAD)

Dilute 10 g (0.045 mol) of ^iPr CpCo (CO) ₂ to 150 mL of ethylcyclohexane and add N, N' -diisopropyl-1,4-diaza-1,3-butadiene ( After adding 6.3 g (0.045 mol) of N, N'- diisopropyl-1,4-diaza-1,3-butadiene, ⁱ Pr ₂ -DAD) at room temperature, the mixed solution was stirred and then refluxed for 4 days. During reflux reaction. After completion of the reaction, the solvent and volatile side reactions were removed under reduced pressure, extracted with normal hexane (n-hexane, C ₆ H ₁₄ ), and filtered through a glass filter to remove the solvent and volatile side reactions under reduced pressure. You get this high dark reddish brown liquid. This liquid was distilled under reduced pressure to obtain 7.2 g (yield: 52.23%) of ^iPr CpCo ( ⁱ Pr ₂ -DAD) as a viscous reddish brown liquid compound.

Elemental Analysis: cacld. for C ₁₆ H ₂₂ N ₂ Co: C, 62.73; H, 8.88; N, 9.14. found: C, 63.21; H, 8.98; N, 9.14.

Boiling Point (b.p): 78 ° C at 0.16torr.

Density: 1.105g / ml at 25 ℃

¹ H-NMR (C ₆ D ₆ ): δ 1.269, 1.285 ([(C H ₃ ) ₂ CHC ₅ H ₄ ] -Co, d, 6H),

δ 1.505, 1.522 ([(C H ₃ ) ₂ CH-N = CHCH = N-CH (C H ₃ ) ₂ ] -Co, d, 12H),

δ 2.821 ([(CH ₃ ) ₂ C H C ₅ H ₄ ] -Co, sept, 1H),

δ 4.292, 4.506 ([(CH ₃ ) ₂ CHC ₅ H ₄ ] -Co, br, br, 2H, 2H),

δ 5.105 ([(CH ₃ ) ₂ C H —N═CHCH = NC H (CH ₃ ) ₂ ] —Co, sept, 2H),

δ 6.962 ([(CH ₃ ) ₂ CH—N═C H C H = N—CH (CH ₃ ) ₂ ] —Co, s, 2H).

¹³ C-NMR (C ₆ D ₆ ): δ 24.304 ([( C H ₃ ) ₂ CHC ₅ H ₄ ] -Co),

δ 25.276 ([[( C H ₃ ) ₂ CH-N = CHCH = N-CH ( C H ₃ ) ₂ ] -Co),

δ 27.088 ([(CH ₃ ) ₂ C HC ₅ H ₄ ] -Co),

δ 63.420 ([(CH ₃ ) ₂ C H-N = CHCH = N- C H (CH ₃ ) ₂ ] -Co),

δ 72.926, 72.954 ([(CH 3) 2 CH-N = C H C H = N-CH (CH 3) 2] -Co),

δ 73.478, 132.786 ([CH ₃ CH ₂ C ₅ H ₄ ] -Co),

Experimental Example 1

TG / DTA analysis was performed for basic thermal characterization of cobalt precursor compounds prepared in Example 1 ( ^Et CpCo ( ⁱ Pr ₂ -DAD)) and Example 2 ( ^iPr CpCo ( ⁱ Pr ₂ -DAD)). It was. At this time, the weight of each precursor sample is about 10mg taken into the alumina sample container and measured to 300 ^o C at a temperature increase rate of 10 ^o C / min is shown in Figures 1 and 2.

As can be seen in FIGS. 1 and 2, the novel cobalt precursor compounds of the present invention do not exhibit exothermic peaks in the DTA graph due to thermal decomposition of the compounds and decompose during vaporization with a final residual amount of less than 5% in the TG graph. It was confirmed that the compound has a characteristic of almost no vaporization.

Experimental Example 2

In order to evaluate the thermal stability over time of the cobalt precursor compounds prepared in Example 1 ( ^Et CpCo ( ⁱ Pr ₂ -DAD)) and Example 2 ( ^iPr CpCo ( ⁱ Pr ₂ -DAD)). TG analysis was performed. At this time, the weight of each precursor sample is about 10mg, put into the alumina sample container, and then ^10o C / min. To 80 ^o C, 100 ^o C, 120 ^o C and 150 ^o C temperature. 3 and 4 show the results obtained by heating at a heating rate of and maintaining 2 hours after reaching each temperature.

As can be seen in Figures 3 and 4, the cobalt precursor compounds prepared in the present invention are all reduced in weight with a constant slope with time at each temperature of 80 ^o C, 100 ^o C, 120 ^o C and 150 ^o C It was confirmed that the evaporation without pyrolysis of a special precursor at a temperature below 150 ^o C. Therefore, the cobalt organometallic precursor compound of the present invention is expected to be used as a precursor useful for organometallic chemical vapor deposition and atomic layer deposition as organic cobalt compounds having excellent thermal stability and liquid at room temperature and excellent vaporization properties.

 Experimental Example 3

Film formation evaluation by CVD process was performed using ^Et CpCo ( ⁱ Pr ₂ -DAD) precursor prepared according to Example 1 among novel cobalt precursors according to the present invention. The substrate used for the deposition was a substrate coated with a 30 nm TiN film, a substrate coated with 100 nm SiO ₂ , and a Si substrate on a Si substrate. The deposition equipment used a pyrex tube with an inner diameter of 5 cm and a length of 30 cm, one end filled with a fresh cobalt source and the other end connected to a vacuum ( ^10-2 torr) pump. Pyrex tube was maintained at a pressure of 120 ~ 300mtorr using a vacuum pump, while the temperature of the precursor is maintained at 100 ℃ constant to evaluate the film-forming properties according to the substrate temperature (a) substrate temperature as shown in Table 1 According to the deposition characteristics according to (b) and the deposition characteristics according to the deposition time, the results are shown in Table 2 and FIGS. 5 to 7.

Precursor: ^Et CpCo ( ⁱ Pr ₂ -DAD) / Substrate: TiN / Si, Si and SiO ₂ Deposition Conditions (a) substrate temperature change (b) Deposition time change Precursor temperature ( ^oC ) 100 ^o C 100 ^o C Substrate temperature ( ^oC ) 250/275/300/350 ^o C 350 ^o C Deposition time 1 hours 20 minutes / 40 minutes / 1 hour

(a) substrate temperature change (b) Deposition time change Substrate temperature
(℃) Thickness (nm) Deposition time
(min) Thickness (nm) TiN SiO ₂ Si TiN SiO ₂ Si 250 x x x 20 24.38 45.92 39.06 275 209.35 27.19 130.03 40 300.67 215.45 421.36 300 150.38 263.75 405.00 60 447.51 350.01 631.78 350 447.51 350.01 631.78

As shown in Table 2, when ^Et CpCo ( ⁱ Pr ₂ -DAD) was used as a precursor, it was confirmed that the cobalt thin film was formed at a temperature of 100 ^o C and a substrate temperature of 275 ^o C or more. FIG. 5 is an SEM image of a cobalt thin film deposited at a source temperature of 100 ° C., a substrate temperature of 275, 300, and 350 ° C. for 1 hour on each substrate, and the thickness of the film is increased by increasing the substrate temperature and the deposition time. As shown in the thickness change graph of the deposited thin film according to the deposition temperature of FIG. 6, the deposition thickness characteristic of each substrate was confirmed, and as the temperature increased, the deposition on the Si substrate was confirmed. 7 shows the surface roughness using AFM, 3.633 nm on TiN surface, 4.409 nm on SiO ₂ surface, 2.587 nm on Si surface (precursor temperature 100 ° C, substrate temperature 350 ° C, deposition time 1 hour). We can see that the surface is fairly smooth.

As a result, the ^Et CpCo ( ⁱ Pr ₂ -DAD) precursor according to Example 1 of the present invention was able to confirm that the film formation performance was excellent only by thermal decomposition without the use of a separate plasma, and showed the possibility of selective deposition on the substrate.

Figure 1 shows a TG / DTA graph of the ^Et CpCo ( ⁱ Pr ₂ -DAD) precursor compound prepared in Example 1 of the present invention.

Figure 2 shows the TG / DTA graph of the ^iPr CpCo ( ⁱ Pr ₂ -DAD) precursor compound prepared in Example 2 of the present invention.

Figure 3 shows an isothermal TG graph of the ^Et CpCo ( ⁱ Pr ₂ -DAD) precursor compound prepared in Example 1 of the present invention.

Figure 4 shows an isothermal TG graph of the ^iPr CpCo ( ⁱ Pr ₂ -DAD) precursor compound prepared in Example 2 of the present invention.

5 is an SEM image of the deposited thin film carried out by Experimental Example 3.

6 is a graph showing a thickness change of the deposited thin film according to the deposition temperature performed by Experimental Example 3. FIG.

7 is an AFM image of the deposited thin film carried out by Experimental Example 3. FIG.

Claims (14)

Organic metal precursor for cobalt metal thin film or cobalt-containing ceramic thin film, characterized in that the organometallic precursor compound used for depositing the cobalt-containing metal thin film and the cobalt-containing ceramic thin film is an organic metal precursor compound Precursor compound. <Formula 1>

In Formula 1 R ¹ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² , and — (CH ₂ ) _n OR ¹³ . alkoxy group represented _{(alkoxyalkyl), - (CH 2} ) are selected from among _n NR ¹⁴ R ¹⁵ dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms. The method according to claim 1, In the organometallic precursor compound represented by Formula 1, R ² to R ⁵ is an organometallic precursor compound represented by the following Formula 2, each of which is hydrogen (H), a cobalt metal thin film or an organic metal for cobalt-containing ceramic thin film deposition Precursor compound. <Formula 2>

In Formula 2, R ¹ and R ⁶ to R ⁹ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, or a trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² . , An alkoxyalkyl group represented by-(CH ₂ ) _n OR ¹³ , or a dialkylaminoalkyl group represented by-(CH ₂ ) _n NR ¹⁴ R ¹⁵ . N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms. The method according to claim 2, In the organometallic precursor compound of Formula 2, R ¹ is an organometallic precursor compound represented by the following Formula 3, which is an ethyl (ethyl) group, the organic metal precursor compound for deposition of cobalt metal thin film or cobalt-containing ceramic thin film. <Formula 3>

R ⁶ to R ⁹ in Formula 3 may each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, a trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² ,-( CH ₂₎ alkoxyalkyl group (alkoxyalkyl) represented by _n OR ^13, - are selected from ^{_{(CH 2) n NR 14 R}} 15 dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms. The method according to claim 3, In the compound of Formula 3, R ⁶ and R ⁷ are both an isopropyl group and cobalt metal thin film or cobalt-containing, characterized in that the organic metal precursor compound represented by the following formula (4) wherein both R ⁸ and R ⁹ are hydrogen groups Organic metal precursor compound for ceramic thin film deposition. <Formula 4>

The method according to claim 2, In the compound of Formula 2, R ¹ is an organometallic precursor compound represented by the following formula (6) isopropyl group (isopropyl) organic metal precursor compound for deposition of cobalt metal thin film or cobalt-containing ceramic thin film. <Formula 5>

R ⁶ to R ⁹ in Formula 3 may each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, a trialkylsilylalkyl represented by (CH ₂ ) _n SiR ¹⁰ R ¹¹ R ¹² ,-( CH ₂₎ alkoxyalkyl group (alkoxyalkyl) represented by _n OR ^13, - are selected from ^{_{(CH 2) n NR 14 R}} 15 dialkylamino group (dialkylaminoalkyl) represented by. N is an integer value of 1 to 4, and R ¹⁰ to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms. The method according to claim 5, In the compound represented by Chemical Formula 6, R ⁶ and R ⁷ are both isopropyl groups and R ⁸ and R ⁹ are all organometallic precursor compounds represented by the following Chemical Formula 7, wherein the cobalt-containing metal thin film or cobalt-containing compound is represented. Organic metal precursor compound for ceramic thin film deposition. <Formula 6>

In order to prepare the organometallic precursor compound of any one of claims 1 to 6, a non-polar solvent such as benzene, hexane, toluene, ethylcyclohexane or the like as shown in Scheme 1 or A 1,4-diaza-2,3-butadiene compound is added to a cyclopentadienyl cobalt dicarbonyl compound at low temperature in a solvent having a weak polarity, and then prepared by distillation under reduced pressure after reflux reaction. A method for preparing an organometallic precursor compound for depositing a cobalt metal thin film or a cobalt-containing ceramic thin film.

R ¹ to R ⁹ in Scheme 1 are as defined in Chemical Formula 1. A thin film forming a metal thin film or metal oxide thin film on a substrate by atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) using an organometallic precursor compound. The vapor deposition method of claim 1, wherein the organometallic precursor compound of claim 1 is used as the organometallic precursor compound. The method according to claim 8, Thin film deposition method characterized in that the deposition temperature is 150 ~ 700 ℃ when depositing on the substrate using the organometallic precursor compound. The method according to claim 8, The organometallic precursor compound using a thermal energy or plasma when the deposition on the substrate, or a thin film deposition method characterized in that applying a bias on the substrate. The method according to claim 8, The transfer method for moving the organometallic precursor compound on a substrate is a thin film, which is selected from a bubbling method, a direct liquid injection (DLI) or a liquid transfer method for dissolving and transporting the precursor compound in an organic solvent. Deposition method. The method according to claim 8, Argon (Ar), nitrogen (N ₂ ), helium (He), hydrogen (H ₂ ), oxygen (O ₂ ) or ammonia (NH ₃ ) as a transport gas or diluent gas for moving the organometallic precursor compound on a substrate Thin film deposition method using one or more mixtures selected from). The method according to claim 8, Thin film deposition method using water vapor (H ₂ O), oxygen (O ₂ ) and ozone (O ₃ ) as a reaction gas for depositing a cobalt-containing metal oxide thin film on the substrate. The method according to claim 8, A thin film deposition method using hydrogen (H ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ) or silane as a reaction gas for depositing a cobalt-containing metal oxide thin film on the substrate. .

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