KR102741165B1 - Organic metal compound, composition for depositing thin film comprising the organic metal compound, manufacturing method for thin film using the composition, thin film manufactured from the composition, and semiconductor device including the thin film - Google Patents

Abstract

상기 화학식 1에서, R¹ 내지 R⁸의 정의는 명세서에 기재한 바와 같다.The present invention relates to an organometallic compound represented by the following chemical formula 1, a composition for thin film deposition comprising the organometallic compound, a method for producing a thin film using the composition for thin film deposition, a thin film produced from the composition for thin film deposition, and a semiconductor device comprising the thin film.
[Chemical Formula 1]

In the above chemical formula 1, the definitions of R ¹ to R ⁸ are as described in the specification.

Description

Organometallic compound, composition for thin film deposition comprising organometallic compound, method for manufacturing thin film using composition for thin film deposition, thin film manufactured from composition for thin film deposition, and semiconductor device including thin film {ORGANIC METAL COMPOUND, COMPOSITION FOR DEPOSITING THIN FILM COMPRISING THE ORGANIC METAL COMPOUND, MANUFACTURING METHOD FOR THIN FILM USING THE COMPOSITION, THIN FILM MANUFACTURED FROM THE COMPOSITION, AND SEMICONDUCTOR DEVICE INCLUDING THE THIN FILM}

The present invention relates to an organometallic compound, a composition for thin film deposition comprising the organometallic compound, a method for producing a thin film using the composition for thin film deposition, a thin film produced from the composition for thin film deposition, and a semiconductor device comprising the thin film.

Recently, the semiconductor industry has been developing from a size of several hundred nanometers to an ultra-fine technology of several to tens of nanometers. In order to realize this ultra-fine technology, thin films with high permittivity and low electrical resistance are essential.

However, due to the high integration of semiconductor devices, it is difficult to form the thin film using a conventional physical vapor deposition process (PVD), such as a sputtering process. Accordingly, recently, the thin film is formed using a chemical vapor deposition process (CVD) or an atomic layer deposition process (ALD).

In order to uniformly form the above thin film by a chemical vapor deposition process (CVD) or an atomic layer deposition process (ALD), a composition for thin film deposition that is easy to vaporize and thermally stable is required.

One embodiment provides an organometallic compound having low viscosity and excellent volatility.

Another embodiment provides a composition for thin film deposition comprising the organometallic compound.

Another embodiment provides a method for producing a thin film using the composition for thin film deposition.

Another embodiment produces a thin film prepared from the composition for thin film deposition.

Another embodiment provides a semiconductor device comprising the thin film.

According to one embodiment, an organometallic compound represented by the following chemical formula 1 is provided.

[Chemical Formula 1]

In the above chemical formula 1,

R ¹ to R ⁸ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by the following chemical formula 2,

Among R ¹ to R ⁸ , one or more and four or fewer are each independently a group represented by the following chemical formula 2,

[Chemical formula 2]

*-L-SiR ^a R ^b R ^c

In the above chemical formula 2,

L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group,

R ^a , R ^b and R ^c are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,

At least one of R ^a , R ^b and R ^c is a substituted or unsubstituted C1 to C5 alkyl group,

* indicates the point where it is connected to cyclopentadiene.

Among the above R ¹ to R ⁸ , one or more and four or fewer are each independently a group represented by the above chemical formula 2,

At least one of the remaining R ¹ to R ⁸ may independently be a substituted or unsubstituted C1 to C10 alkyl group.

At least one of the remaining R ¹ to R ⁸ may each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

One or both of the above R ¹ to R ⁴ are each independently a group represented by the above chemical formula 2,

One or both of the above R ⁵ to R ⁸ can each be independently expressed by the above chemical formula 2.

The above chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-5.

[Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[Chemical Formula 1-4] [Chemical Formula 1-5]

In the chemical formulas 1-1 to 1-5 above,

R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group,

R ^a1 to R ^a4 , R ^b1 to R ^b4 , and R ^c1 to R ^c4 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,

At least one of R ^a1 , R ^b1 and R ^c1 ; at least one of R ^a2 , R ^b2 and R ^c2 ; at least one of R ^a3 , R ^b3 and R ^c3 ; and at least one of R ^a4 , R ^b4 and R ^c4 is a substituted or unsubstituted C1 to C5 alkyl group.

At least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ in the chemical formulas 1-1 to 1-5 may independently be a substituted or unsubstituted C1 to C10 alkyl group.

At least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ in the above chemical formulae 1-1 to 1-5 may independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

The above organometallic compound may be liquid at room temperature.

The above organometallic compound may have a viscosity of 400 cps or less as measured under the following conditions.

[Viscosity measurement conditions]

ㆍ Viscosity measuring instrument: RVDV-Ⅱ (BROOKFIELD)

ㆍ Spindle No.: CPA-40z

ㆍTorque/RPM: 20~80% Torque/ 1-100 RPM

ㆍ Measurement temperature (sample cup temperature): 25℃

The temperature at which the organometallic compound experiences a weight loss of 50% compared to its initial weight when measured by thermogravimetric analysis under an argon gas atmosphere at 1 atm may be 50°C to 300°C.

According to another embodiment, a composition for thin film deposition is provided comprising an organometallic compound according to one embodiment.

The above composition for thin film deposition may be a first composition for thin film deposition.

According to another embodiment, a method for manufacturing a thin film is provided, comprising the steps of vaporizing a first thin film deposition composition according to one embodiment, and depositing the vaporized first thin film deposition composition on a substrate.

The method for manufacturing the above thin film comprises the steps of vaporizing a second thin film deposition composition, and

The method further comprises a step of depositing the vaporized second thin film deposition composition on the substrate, wherein the second thin film deposition composition may include a second organometallic compound including titanium, zirconium, hafnium, niobium, tantalum, or a combination thereof.

The above-described vaporized first thin film deposition composition and the above-described vaporized second thin film deposition composition can be deposited together or independently on the substrate.

The step of vaporizing the first thin film deposition composition may include a step of heat treating the first thin film deposition composition at a temperature of 300°C or less.

The step of depositing the vaporized first thin film deposition composition on the substrate further includes the step of reacting the vaporized first thin film deposition composition with a reaction gas, and the reaction gas may include water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), plasma, hydrogen peroxide (H ₂ O ₂ ), ammonia (NH ₃ ), or hydrazine (N ₂ H ₄ ), or a combination thereof.

The step of depositing the vaporized first thin film deposition composition on the substrate can be performed using atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD).

According to another embodiment, a thin film is provided manufactured from a composition for thin film deposition according to one embodiment.

According to another embodiment, a semiconductor device including a thin film according to one embodiment is provided.

The organometallic compound according to one embodiment is in a liquid state at room temperature, exhibits low viscosity, and has excellent volatility. Therefore, a semiconductor thin film can be easily manufactured using the organometallic compound according to one embodiment, and a semiconductor device having high reliability in electrical characteristics can be provided by including the manufactured thin film.

Figure 1 is a temperature-weight change rate graph showing the weight change rate according to temperature of the organometallic compounds according to Examples 1 and 2 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Unless otherwise specifically defined herein, when a part such as a layer, film, thin film, region, or plate is said to be “on” or “over” another part, this includes not only cases where it is “directly on” the other part, but also cases where there is another part in between.

Hereinafter, in this specification, unless otherwise specifically defined, “combination thereof” means a mixture, complex, coordination compound, layered product, alloy, etc. of components.

Hereinafter, unless otherwise specifically defined, "substitution" means a hydrogen atom substituted with deuterium, a halogen group, a hydroxy group, a cyano group, a nitro group, -NRR' (wherein, R and R' are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), -SiRR'R" (wherein, R, R', and R" are each independently hydrogen, a substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), a C1 to C20 alkyl group, a C1 to C10 It means substituted with a haloalkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, or a combination thereof. "Unsubstituted" means that a hydrogen atom is not replaced by another substituent and remains a hydrogen atom.

As used herein, “hetero” means, unless otherwise defined, containing 1 to 3 heteroatoms selected from the group consisting of N, O, S and P in one functional group, the remainder being carbon.

As used herein, "alkyl group" means a linear or branched aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double bond or triple bond. The alkyl group may be a C1 to C20 alkyl group. For example, the alkyl group may be a C1 to C10 alkyl group, a C1 to C8 alkyl group, a C1 to C6 alkyl group, or a C1 to C4 alkyl group. For example, the C1 to C4 alkyl group may be a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl group.

As used herein, unless otherwise defined, “saturated aliphatic hydrocarbon group” means a hydrocarbon group in which a bond between carbon atoms in a molecule is formed by a single bond. The saturated aliphatic hydrocarbon group may be a C1 to C20 saturated aliphatic hydrocarbon group. For example, the saturated aliphatic hydrocarbon group may be a C1 to C10 saturated aliphatic hydrocarbon group, a C1 to C8 saturated aliphatic hydrocarbon group, a C1 to C6 saturated aliphatic hydrocarbon group, a C1 to C4 saturated aliphatic hydrocarbon group, or a C1 to C2 saturated aliphatic hydrocarbon group. For example, the C1 to C6 saturated aliphatic hydrocarbon group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a 2,2-dimethylpropyl group, or a tert-butyl group.

As used herein, “organometallic compound” means a compound containing a chemical bond between a metal element and a carbon, oxygen, or nitrogen element, wherein the chemical bond means a covalent bond, an ionic bond, and a coordinate bond.

As used herein, “ligand” means a molecule or ion that chemically bonds around a metal ion, wherein the molecule may be an organic molecule, and wherein the chemical bond includes a covalent bond, an ionic bond, and a coordinate bond.

In this specification, viscosity is based on measurements made under the following measurement conditions.

[Viscosity measurement conditions]

ㆍ Viscosity measuring instrument: RVDV-Ⅱ (BROOKFIELD)

ㆍ Spindle No.: CPA-40z

ㆍTorque/RPM: 20~80% Torque/ 1-100 RPM

ㆍ Measurement temperature (sample cup temperature): 25℃

In order to manufacture a thin film having high permittivity and high capacitance by a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process, an organometallic compound including an alkaline earth metal and one or more organic ligands bonded to the alkaline earth metal is used. The alkaline earth metal refers to a Group IIA element and may include, for example, strontium, barium, or a combination thereof, and the organic ligand may be derived from cyclopentadiene substituted with at least one substituted or unsubstituted C1 to C20 alkyl group. However, since most of the organometallic compounds are solids or have low vapor pressures, it is difficult to uniformly form a thin film by a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD). Therefore, an organometallic compound having high permittivity and high capacitance, as well as being easy to vaporize and thermally stable, is required.

One embodiment provides an organometallic compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

R ¹ to R ⁸ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by the following chemical formula 2,

Among R ¹ to R ⁸ , one or more and four or fewer are each independently a group represented by the following chemical formula 2,

[Chemical formula 2]

*-L-SiR ^a R ^b R ^c

In the above chemical formula 2,

L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group,

R ^a , R ^b and R ^c are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,

At least one of R ^a , R ^b and R ^c is a substituted or unsubstituted C1 to C5 alkyl group,

* indicates the point where it is connected to cyclopentadiene.

R ^a , R ^b and R ^c may be equal or different.

In the above chemical formula 2, a plurality of R ^a , R ^b and R ^c may be the same or different.

An organometallic compound according to one embodiment comprises an organic ligand derived from cyclopentadiene around an organometal strontium (Sr) and including at least one substituted or unsubstituted alkylsilyl group, specifically, 1 to 4 substituted or unsubstituted alkylsilyl groups, thereby reducing the lattice energy of the organometallic compound, preventing stacking interactions between organometallic compounds, thereby reducing the attractive force between organometallic compounds, and thereby providing an organometallic compound that is a low-viscosity liquid at room temperature and has excellent volatility. Therefore, the organometallic compound according to one embodiment can be advantageously used as a deposition composition for producing a thin film. In addition, the deposition composition manufactured as described above exhibits a high dielectric constant, and thus can provide a thin film exhibiting high capacitance.

Although not bound by a specific theory, the organometallic compound represented by the above chemical formula 1 can be viewed as one in which the organometallic Sr is either single-bonded to one of the carbon atoms forming the five-membered ring of cyclopentadiene, or bonded to a pair of electrons delocalized on five carbon atoms forming the five-membered ring of cyclopentadiene.

Meanwhile, the compound represented by the above chemical formula 1 includes a group represented by the above chemical formula 2 as a substituent of cyclopentadiene, and specifically, the group represented by the above chemical formula 2 may be included in a number of 1 to 4. The alkylsilyl group represented by the above chemical formula 2 is a substituent having a relatively strong electron donating characteristic compared to an alkyl group, and can further push electrons to the carbon (C) of cyclopentadiene in the above organometallic compound and the organometallic Sr bond, thereby improving the stability of the organometallic compound.

In addition, since the Si element has a larger atomic size than the C element, it can have a higher steric hindrance effect, and is therefore effective in controlling intermolecular aggregation.

Accordingly, the stability of the organometallic compound can be improved, the viscosity of the composition for thin film deposition can be further reduced, and the volatility can be further improved.

As a non-limiting example, one to four of R ¹ to R ⁸ of the chemical formula 1 are each independently a group represented by the chemical formula 2, and at least one of the remaining R ¹ to R ⁸ can each independently be a substituted or unsubstituted C1 to C10 alkyl group.

For example, at least one of the remaining R ¹ to R ⁸ can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group, or a tert-hexyl group.

In one embodiment, at least one of the remaining R ¹ to R ⁸ can each independently be a substituted or unsubstituted C3 to C6 branched alkyl group, for example, a substituted or unsubstituted C3 to C6 iso-alkyl group, a substituted or unsubstituted C3 to C6 sec-alkyl group, a substituted or unsubstituted C4 to C6 tert-alkyl group, or a substituted or unsubstituted C5 to C6 neo-alkyl group.

For example, at least one of R ¹ to R ⁸ can each independently be an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

R ¹ to R ⁸ may be the same or different.

For example, R ^a , R ^b and R ^c are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and any one of R ^a , R ^b and R ^c may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a , R ^b and R ^c are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and two of R ^a , R ^b and R ^c may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a , R ^b and R ^c may each independently be a substituted or unsubstituted C1 to C5 alkyl group.

More specifically, at least one of R ^a , R ^b and R ^c can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

R ^a , R ^b and R ^c may be equal or different.

A plurality of R ^a , R ^b and R ^c may be the same or different.

As a non-limiting example, one or both of R ¹ to R ⁴ may each independently be a group represented by the chemical formula 2, and one or both of R ⁵ to R ⁸ may each independently be a group represented by the chemical formula 2.

For example, the organometallic compound represented by the above chemical formula 1 may have a symmetrical structure with cyclopentadienes positioned above and below Sr. An organometallic compound with such a symmetrical structure may have lower viscosity and higher volatility compared to an organometallic compound with an asymmetrical structure.

In one embodiment, the chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-5.

[Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[Chemical Formula 1-4] [Chemical Formula 1-5]

In the chemical formulas 1-1 to 1-5 above,

R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group,

R ^a1 to R ^a4 , R ^b1 to R ^b4 , and R ^c1 to R ^c4 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,

At least one of R ^a1 , R ^b1 and R ^c1 ; at least one of R ^a2 , R ^b2 and R ^c2 ; at least one of R ^a3 , R ^b3 and R ^c3 ; and at least one of R ^a4 , R ^b4 and R ^c4 is a substituted or unsubstituted C1 to C5 alkyl group.

In the above Chemical Formulas 1-1 to 1-5, at least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ may each independently be a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C1 to C8 alkyl group, for example, a substituted or unsubstituted C1 to C6 alkyl group.

For example, at least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, or an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

The above R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ may each independently be, for example, a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C3 to C10 alkyl group, but are not limited thereto.

Accordingly, the above R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, or an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

At least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ may be a substituted or unsubstituted C3 to C6 branched alkyl group, for example, a substituted or unsubstituted C3 to C6 iso-alkyl group, a substituted or unsubstituted C3 to C6 sec-alkyl group, a substituted or unsubstituted C4 to C6 tert-alkyl group, or a substituted or unsubstituted C5 to C6 neo-alkyl group.

For example, at least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ may be an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ may be the same or different.

For example, R ^a1 , R ^b1 and R ^c1 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and any one of R ^a1 , R ^b1 and R ^c1 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a1 , R ^b1 and R ^c1 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and two of R ^a1 , R ^b1 and R ^c1 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a1 , R ^b1 and R ^c1 may each independently be a substituted or unsubstituted C1 to C5 alkyl group.

More specifically, at least one of R ^a1 , R ^b1 and R ^c1 can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

For example, R ^a2 , R ^b2 and R ^c2 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and any one of R ^a2 , R ^b2 and R ^c2 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a2 , R ^b2 and R ^c2 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and two of R ^a2 , R ^b2 and R ^c2 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a2 , R ^b2 and R ^c2 may each independently be a substituted or unsubstituted C1 to C5 alkyl group.

More specifically, at least one of R ^a2 , R ^b2 and R ^c2 can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

For example, R ^a3 , R ^b3 and R ^c3 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and any one of R ^a3 , R ^b3 and R ^c3 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a3 , R ^b3 and R ^c3 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and two of R ^a3 , R ^b3 and R ^c3 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a3 , R ^b3 and R ^c3 may each independently be a substituted or unsubstituted C1 to C5 alkyl group.

More specifically, at least one of R ^a3 , R ^b3 and R ^c3 can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

For example, R ^a4 , R ^b4 and R ^c4 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and any one of R ^a4 , R ^b4 and R ^c4 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a4 , R ^b4 and R ^c4 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group, and two of R ^a4 , R ^b4 and R ^c4 may be a substituted or unsubstituted C1 to C5 alkyl group. In addition, for example, R ^a4 , R ^b4 and R ^c4 may each independently be a substituted or unsubstituted C1 to C5 alkyl group.

More specifically, at least one of R ^a4 , R ^b4 and R ^c4 can each independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.

R ^a1 , R ^a2 , R ^a3 and R ^a4 may be the same or different.

R ^b1 , R ^b2 , R ^b3 and R ^b4 may be equal or different.

R ^c1 , R ^c2 , R ^c3 and R ^c4 can be equal or different.

For example, the organometallic compound may be liquid at room temperature (e.g., about 20 ± 5°C, 1 atm). Accordingly, transport of the organometallic compound through a fluid channel (Liquid Delivery System, LDS process) may be easy.

For example, the organometallic compound may have a viscosity measured under the following conditions of about 400 cps or less, for example, about 10 cps to 400 cps, about 10 cps to 300 cps, or about 10 cps to 200 cps. Accordingly, the organometallic compound may be easily transported through the fluid channel without a separate heating or heat preservation process.

[Viscosity measurement conditions]

ㆍ Viscosity measuring instrument: RVDV-Ⅱ (BROOKFIELD)

ㆍ Spindle No.: CPA-40z

ㆍTorque/RPM: 20~80% Torque/ 1-100 RPM

ㆍ Measurement temperature (sample cup temperature): 25℃

For example, when performing thermogravimetric analysis at 1 atm under an Ar (argon) gas atmosphere, the temperature at which a weight loss of 50% compared to the initial weight of the organometallic compound occurs may be, for example, about 50°C to 300°C, about 50°C to 270°C, about 50°C to 250°C, or about 50°C to 200°C.

According to another embodiment, a composition for thin film deposition is provided comprising an organometallic compound according to one embodiment.

The above composition for thin film deposition may contain one or more organometallic compounds represented by the chemical formula 1 described above.

The above composition for thin film deposition may or may not further contain a compound other than the organometallic compound represented by the above-described chemical formula 1, but preferably, it may not further contain a compound other than the organometallic compound represented by the above-described chemical formula 1.

When the composition for thin film deposition further includes a compound other than the organometallic compound, the organometallic compound and the other compound may be a compound containing a non-shared electron pair, for example, the non-shared electron pair-containing compound may include at least one non-shared electron pair. In addition, the compound containing a non-shared electron pair may include at least one heteroatom, for example, the compound containing a non-shared electron pair may include one or two heteroatoms. Here, the heteroatom may be N, O, S, or a combination thereof. Accordingly, the stability of the organometallic compound may be improved, the viscosity of the composition for thin film deposition may be further reduced, and the volatility may be further improved.

For example, the unshared electron pair containing compound can be an alkylamine type, an alkylphosphine type, an alkylamine oxide type, an alkylphosphine oxide type, an ether type, a thioether type, or a combination thereof. For example, the unshared electron pair containing compound can be, but is not limited to, a tertiary alkylamine, a tertiary alkylphosphine, a tertiary alkylamine oxide, a tertiary alkylphosphine oxide, a dialkyl ether, a dialkyl thioether, or a combination thereof.

For example, when the composition for thin film deposition further includes a compound other than the organometallic compound, the organometallic compound may be included in an amount of 10 wt% to 90 wt% based on the total weight of the composition for thin film deposition, for example, 15 wt% to 80 wt%, 20 wt% to 70 wt%, or 25 wt% to 65 wt%.

For example, when the thin film deposition composition further includes a compound other than the organometallic compound, when performing thermogravimetric analysis at 1 atm under an Ar (argon) gas atmosphere, the temperature at which a 50% weight loss compared to the initial weight of the thin film deposition composition occurs may be lower than the temperature at which a 50% weight loss compared to the initial weight of the organometallic compound occurs and the temperature at which a 50% weight loss compared to the initial weight of the unshared electron pair-containing compound occurs. That is, the volatility of the thin film deposition composition may be higher than the volatility of each of the organometallic compounds and the unshared electron pair-containing compound included in the thin film deposition composition. Accordingly, the thin film deposition composition can be easily vaporized and deposited at a relatively low temperature, and can form a uniform thin film.

The above-described composition for thin film deposition may further include a compound other than the above-described organometallic compound and the above-described unshared electron pair-containing compound.

The above-described composition for thin film deposition may be a first composition for thin film deposition.

According to another embodiment, a method for manufacturing a thin film is provided, comprising the steps of vaporizing a first thin film deposition composition, and depositing the vaporized first thin film deposition composition on a substrate.

For example, the step of vaporizing the first thin film deposition composition may include the step of providing the first thin film deposition composition to a first reactor, and the step of providing the first thin film deposition composition to the first reactor may include providing the first thin film deposition composition to the first reactor through a fluid channel.

For example, the step of vaporizing the first thin film deposition composition may include a step of heat treating the first thin film deposition composition at a temperature of 300° C. or less.

For example, the method for manufacturing the thin film may further include a step of vaporizing a second thin film deposition composition, and a step of depositing the vaporized second thin film deposition composition on the substrate.

The second thin film deposition composition may include a second organometallic compound including titanium, zirconium, hafnium, niobium, tantalum, or a combination thereof, and the second organometallic compound may include an alkoxide-based ligand, an alkyl amide-based ligand, a cyclopentadiene-based ligand, a β-diketonate-based ligand, a pyrrole-based ligand, an imidazole-based ligand, an amidinate-based ligand , or a combination thereof.

The second thin film deposition composition may or may not further include a solvent other than the second organometallic compound, and when the second organometallic compound does not further include a solvent, the second organometallic compound may be in a liquid state at room temperature, for example, about 20 ± 5° C., 1 atm. When the second thin film deposition composition further includes a solvent, the solvent may be an organic solvent, for example, a polar solvent such as diethyl ether, petroleum ether, tetrahydrofuran, or 1,2-dimethoxyethane. When the organic solvent is included, it may be included in a molar ratio twice that of the organometallic compound. Accordingly, the organometallic compound included in the thin film deposition composition may be coordinated by the organic solvent, thereby improving the stability of the organometallic compound, and thus suppressing a central metal atom included in the organometallic compound from reacting with other organometallic compounds around it to form an oligomer. In addition, a composition for thin film deposition containing an organic solvent can further increase the vapor pressure of an organometallic compound existing as a single molecule.

For example, the step of vaporizing the second thin film deposition composition may include the step of providing the second thin film deposition composition to the first reactor, or to a second reactor different from the first reactor (via a fluid channel).

For example, the step of vaporizing the second thin film deposition composition may include a step of heat treating the second thin film deposition composition at a temperature of 200° C. or less, for example, a step of heat treating the second thin film deposition composition at a temperature of about 30° C. to 200° C., about 30° C. to 175° C., or about 30° C. to 150° C.

For example, the first thin film deposition composition and the second thin film deposition composition may be vaporized together or independently of each other. When the first thin film deposition composition and the second thin film deposition composition are vaporized independently of each other, the vaporized first thin film deposition composition and the vaporized second thin film deposition composition may be deposited together or independently of each other on the substrate, for example, may be deposited alternately.

For example, the step of depositing the vaporized first thin film deposition composition on the substrate may further include a step of reacting the vaporized first thin film deposition composition with a reaction gas, and the step of depositing the vaporized second thin film deposition composition on the substrate may further include a step of reacting the vaporized second thin film deposition composition with the reaction gas.

For example, the reactant gas can be an oxidizing agent, such as water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), plasma, hydrogen peroxide (H ₂ O ₂ ), ammonia (NH ₃ ), or hydrazine (N ₂ H ₄ ), or a combination thereof.

The deposition method is not particularly limited, but the method for manufacturing the above-described thin film can be performed using Atomic Layer Deposition (ALD) or Metal Organic Chemical Vapor Deposition (MOCVD). Specifically, the step of depositing the vaporized first thin film deposition composition and/or the vaporized second thin film deposition composition on the substrate can be performed using Atomic Layer Deposition (ALD) or Metal Organic Chemical Vapor Deposition (MOCVD).

For example, the step of depositing the vaporized first thin film deposition composition and/or the vaporized second thin film deposition composition on the substrate may be performed at a temperature of 100° C. to 1000° C.

According to another embodiment, a thin film is provided, which is manufactured from a composition for thin film deposition according to one embodiment. The thin film can be manufactured by a method for manufacturing a thin film according to one embodiment.

For example, the thin film can be a perovskite thin film, and for example, the thin film can include a strontium titanium oxide-based film, a barium strontium titanium oxide-based film, a rubidium strontium oxide-based film, or a combination thereof. Specifically, the thin film can include SrTiO ₃ , Ba- _x Sr _1-x TiO ₃ (wherein, x is 0.1 to 0.9), SrRuO _{3 ,} SrcCeO ₃ or a combination thereof.

For example, the thickness of the thin film may be less than about 10 nm, and the dielectric constant value of the thin film may be about 50 or more, for example, about 110 or more. Accordingly, the thin film may have a uniform thickness and excellent leakage current characteristics while forming a fine pattern.

The above thin film can be a uniform thin film exhibiting high permittivity and high electric capacity, and can exhibit excellent insulating properties. Accordingly, the thin film can be an insulating film, and the insulating film can be included in an electrical or electronic device. The electrical or electronic device can be a semiconductor device, and the semiconductor device can be, for example, a dynamic random-access memory (DRAM).

According to another embodiment, a semiconductor device including a thin film according to one embodiment is provided. The semiconductor device can have improved electrical characteristics and reliability by including the thin film according to one embodiment.

The above-described implementation examples are described in more detail through the following examples. However, the following examples are for the purpose of explanation only and do not limit the scope of rights.

Synthesis of organometallic compounds

Hereinafter, the organometallic oxide and metal-silicon oxide thin film deposition organometallic precursor compounds and thin film deposition methods according to the present invention will be described in more detail through the following examples and experimental examples. However, these are presented only to help understand the present invention, and the present invention is not limited to the following examples and experimental examples.

Example 1

Strontium metal (10.61 g, 0.121 mol), a compound represented by the following chemical formula a (61.96 g, 0.279 mol), and 300ml of tetrahydrofuran (THF) Place in a flame-dried flask and cool to -78°C. High-purity ammonia gas (>5N) was slowly added over 2 hours. Afterwards, the temperature was slowly increased to room temperature over 5 hours, the excess ammonia gas was removed, and the mixture was stirred under argon gas for 24 hours. Under reduced pressure, THF was completely removed while heating to 50℃. By distillation under reduced pressure, an organometallic compound represented by the following chemical formula 2A was obtained. (Yield: 51.9%, viscosity 395 cps)

¹ H NMR (Bruker Ultraspin 300MHZ, C6D6): δ 0.08 (Si-CH3,S,18H), δ 1.17,1.23 (i-Pr(CH-CH3),m,24H), δ 2.73 (i-PrCp( CH), m,4H), δ5.52 (Cp(CH2),s,4H)

[chemical formula a]

[Chemical Formula 2A]

Example 2

An organometallic compound represented by the following chemical formula 2B was obtained in the same manner as in Example 1, except that a compound represented by the following chemical formula b (65.45 g, 0.278 mol) was used instead of the compound represented by the above chemical formula a. (Yield: 51.9%, viscosity 380 cps)

¹ H NMR (Bruker Ultraspin 300MHZ, C6D6): δ 0.08 (Si-CH ₃ ,S,12H), δ 0.71(Si-CH ₂ ,q,4H), δ 0.89 (-CH ₂ -CH ₃ , t, 6H), δ 1.18,1.25 (i-Pr(CH-CH ₃ ),m,24H), δ 2.76 (i-PrCp(CH), m,4H), δ5.59 (Cp(CH ₂ ), s,4H)

[chemical formula b]

[Chemical Formula 2B]

Comparative Example 1

An organometallic compound represented by the following chemical formula 2C was obtained in the same manner as in Example 1, except that strontium metal (2 g, 0.023 mol) was used and a compound represented by the following chemical formula c (10.1 g, 0.053 mol) was used instead of the compound represented by the above chemical formula a. (Yield 57.1%, powder form)

¹ H NMR (Bruker Ultraspin 300MHZ, C6D6): δ 1.22, 1.30 (i-Pr(CH-CH ₃ ), m, 36H), δ 2.88 (i-PrCp(CH), m, 6H), δ 5.63 (Cp(CH ₂ ), s, 3H), δ 5.81, 5.82 (Cp(CH), d, 0.5H) (Here, Cp represents cyclopentadiene, i represents iso, and Pr represents propyl group, respectively.)

[chemical formula c]

[Chemical Formula 2C]

Rating 1

The molecular weight, phase, and viscosity of the organometallic compounds according to Examples 1, 2, and Comparative Example 1 were measured at room temperature (about 20 ± 5°C, 1 atm), and are shown in Table 1 below.

The viscosity measurement conditions are as follows.

ㆍ Viscosity measuring instrument: RVDV-Ⅱ (BROOKFIELD)

ㆍ Spindle No.: CPA-40z

ㆍTorque/RPM: 20~80% Torque/ 1-100 RPM

ㆍ Measurement temperature (sample cup temperature): 25℃

Molecular weight Condition at room temperature Viscosity (cps) Example 1 530.5 liquid 395 Example 2 558.6 liquid 380 Comparative Example 1 470.3 solid 910

Referring to Table 1 above, it can be confirmed that the organometallic compound according to Comparative Example 1 is a solid at room temperature, whereas the organometallic compounds according to Examples 1 and 2 are liquid at 25°C, and the organometallic compounds according to Examples 1 and 2 have a low viscosity of less than 400 cps.

Rating 2

The volatility of the organometallic compounds according to Examples 1, 2, and Comparative Example 1 is evaluated by thermogravimetric analysis (TGA) at 1 atm as a function of temperature.

Each of the organometallic compounds according to Examples 1, 2, and Comparative Example 1 was placed in an alumina sample container in an amount of 20±2 mg, and the temperature was increased to 500°C at a rate of 10°C/min., and the weight change rate of each organometallic compound according to temperature was measured.

The above weight change rate is a value calculated using the following calculation formula 1.

[Calculation formula 1]

Weight change rate (%) = (weight after heat treatment/initial weight) x 100%

Figure 1 is a temperature-weight change rate graph showing the weight change rate according to temperature of the organometallic compounds according to Examples 1 and 2 and Comparative Example 1.

Referring to FIG. 1, it can be confirmed that the temperature when the weight change rate of the organometallic compounds according to Examples 1 and 2 is 50% is lower than the temperature when the weight change rate of the organometallic compound according to Comparative Example 1 is 50%. Accordingly, it can be confirmed that the volatility of the organometallic compounds according to Examples 1 and 2 is superior to that of the organometallic compound according to Comparative Example 1.

In summary, referring to Table 1 and Figure 1, the organometallic compounds according to Examples 1 and 2 are liquids at room temperature and have excellent volatility, so they are easy to transport through fluid channels and can be easily vaporized and deposited at relatively low temperatures.

Manufacturing of thin films

The organometallic compounds according to Examples 1 and 2 above were charged into a 300 cc bubbler-type canister (200 g), and a thin film was manufactured using ALD equipment.

In order to sufficiently supply the above organometallic compound, the canister was heated to 50 to 150°C, and in order to prevent the organometallic compound from condensing in the pipe, the pipe was heated to 10°C or higher than the canister temperature. At this time, high-purity (99.999%) Ar gas was used as a carrier gas, and the composition for thin film deposition was supplied while flowing the Ar gas at 50 to 500 sccm. Thereafter, ozone gas was flowed at 100 to 500 sccm as an oxidizing reaction gas, and a thin film was deposited on the silicon substrate while changing the temperature of the silicon substrate to 200 to 450°C. The deposited thin film was heat-treated at 650°C for several minutes using RTA (rapid thermal anneal) equipment.

The growth rate per cycle (GPC) of the manufactured thin film was 1.05±0.05Å/cycle, the thickness uniformity (non-uniformity) was 5.0±0.5%, and a crystalline phase was observed in the thin film grown at 340°C or higher.

Although specific embodiments of the present invention have been described and illustrated above, it will be apparent to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Accordingly, such modifications or variations should not be understood individually from the technical spirit or perspective of the present invention, and the modified embodiments should fall within the scope of the claims of the present invention.

Claims (19)

An organometallic compound represented by the following chemical formula 1:
[Chemical Formula 1]

In the above chemical formula 1,
R ¹ to R ⁸ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by the following chemical formula 2,
Among R ¹ to R ⁸ , one or more and four or fewer are each independently a group represented by the following chemical formula 2,
At least one of the remaining R ¹ to R ⁸ is independently a substituted or unsubstituted C1 to C10 alkyl group,
[Chemical formula 2]
*-L-SiR ^a R ^b R ^c
In the above chemical formula 2,
L is a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group,
R ^a , R ^b and R ^c are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,
At least one of R ^a , R ^b and R ^c is a substituted or unsubstituted C1 to C5 alkyl group,
* indicates the point where it is connected to cyclopentadiene.
delete In paragraph 1,
An organometallic compound wherein at least one of the remaining R ¹ to R ⁸ is each independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group, or a tert-hexyl group.
In paragraph 1,
One or both of the above R ¹ to R ⁴ are each independently a group represented by the above chemical formula 2,
An organometallic compound, wherein one or both of the above R ⁵ to R ⁸ are each independently a group represented by the above chemical formula 2.
In paragraph 1,
The above chemical formula 1 is an organometallic compound represented by any one of the following chemical formulas 1-1 to 1-5:
[Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3]

[Chemical Formula 1-4] [Chemical Formula 1-5]

In the chemical formulas 1-1 to 1-5 above,
R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
At least one of R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ is independently a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group,
R ^a1 to R ^a4 , R ^b1 to R ^b4 , and R ^c1 to R ^c4 are each independently hydrogen or a substituted or unsubstituted C1 to C5 alkyl group,
At least one of R ^a1 , R ^b1 and R ^c1 ; at least one of R ^a2 , R ^b2 and R ^c2 ; at least one of R ^a3 , R ^b3 and R ^c3 ; and at least one of R ^a4 , R ^b4 and R ^c4 is a substituted or unsubstituted C1 to C5 alkyl group.
delete In Article 5,
An organometallic compound wherein at least one of the above R ¹ , R ³ , R ⁵ , R ⁷ and R ⁸ is each independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, an iso-butyl group, an iso-pentyl group, a sec-butyl group, a sec-pentyl group, a sec-hexyl group, a tert-butyl group, a tert-pentyl group or a tert-hexyl group.
In paragraph 1,
The above organometallic compound is an organometallic compound that is liquid at room temperature.
In paragraph 1,
An organometallic compound having a viscosity of 400 cps or less as measured under the following conditions.
[Viscosity measurement conditions]
ㆍ Viscosity measuring instrument: RVDV-Ⅱ (BROOKFIELD)
ㆍ Spindle No.: CPA-40z
ㆍTorque/RPM: 20~80% Torque/ 1-100 RPM
ㆍ Measurement temperature (sample cup temperature): 25℃
In paragraph 1,
An organometallic compound having a temperature of 50°C to 300°C at which a weight loss of 50% occurs compared to the initial weight of the organometallic compound when measured by thermogravimetric analysis at 1 atm under an argon gas atmosphere.
A composition for thin film deposition comprising an organometallic compound according to any one of claims 1, 3 to 5, and 7 to 10.
A step of vaporizing a first thin film deposition composition according to Article 11, and
A method for manufacturing a thin film, comprising the step of depositing the vaporized first thin film deposition composition on a substrate.
In Article 12,
The method for manufacturing the above thin film comprises the steps of vaporizing a second thin film deposition composition, and
Further comprising a step of depositing the vaporized second thin film deposition composition on the substrate,
A method for producing a thin film, wherein the second thin film deposition composition comprises a second organometallic compound including titanium, zirconium, hafnium, niobium, tantalum, or a combination thereof.
In Article 13,
A method for manufacturing a thin film, wherein the vaporized first thin film deposition composition and the vaporized second thin film deposition composition are deposited together or independently on the substrate.
In Article 12,
A method for manufacturing a thin film, wherein the step of vaporizing the first thin film deposition composition includes the step of heat-treating the first thin film deposition composition at a temperature of 300° C. or less.
In Article 12,
The step of depositing the vaporized first thin film deposition composition on the substrate further includes the step of reacting the vaporized first thin film deposition composition with a reaction gas,
A method for manufacturing a thin film, wherein the above reaction gas comprises water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), plasma, hydrogen peroxide (H ₂ O ₂ ), ammonia (NH ₃ ), or hydrazine (N ₂ H ₄ ), or a combination thereof.
In Article 12,
A method for manufacturing a thin film, wherein the step of depositing the vaporized first thin film deposition composition on a substrate is performed using atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD).
A thin film manufactured from a composition for thin film deposition according to claim 11.
A semiconductor device comprising a thin film according to claim 18.