Composition for thin film deposition, thin film manufacturing method, thin film and semiconductor device

Abstract

The present invention discloses a composition for depositing a thin film, comprising an organic metal compound containing strontium, barium or a combination thereof and at least one compound containing a non-shared electron pair represented by Chemical Formula 1; a method for manufacturing a thin film using the composition for depositing a thin film; and a thin film manufactured from the composition for depositing a thin film; and a semiconductor device including the thin film. In Formula 1, the definitions of R1 to R3 are as described in the present specification. [Chemical Formula 1] R 1 R 2 R 3 N

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0125525 filed on October 10, 2019, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed are a composition for depositing a thin film, a method for manufacturing a thin film using the composition, a thin film manufactured using the composition for depositing a thin film, and a semiconductor device including the thin film. Background Art

[0004] In recent years, the semiconductor industry has developed from a few hundred nanometers to ultra-fine technology of a few nanometers to tens of nanometers. To achieve this ultra-fine technology, a thin film with a high dielectric constant and low resistance is necessary.

[0005] However, due to the high integration of semiconductor devices, it is difficult to form thin films using the physical vapor deposition (PVD) process (such as sputtering process) used in the past. Therefore, in recent years, chemical vapor deposition (CVD) process or atomic layer deposition (ALD) process is used to form thin films.

[0006] In order to uniformly form a thin film using a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process, a composition for depositing a thin film that is easily vaporized and thermally stable is required. Summary of the invention

[0007] One embodiment provides a composition for depositing a thin film having low viscosity and improved volatility.

[0008] Another embodiment provides a method of manufacturing a thin film using the composition for depositing a thin film.

[0009] Another embodiment provides a thin film produced from the composition for depositing a thin film.

[0010] Another embodiment provides a semiconductor device including a thin film.

[0011] According to one embodiment, a composition for depositing a thin film includes: an organic metal compound including strontium, barium or a combination thereof; and at least one compound represented by Chemical Formula 1 containing an unshared electron pair.

[0012] [Chemical formula 1]

[0013] R 1 R 2 R 3 N

[0014] In Chemical Formula 1, R 1 to R 3 are independently substituted or unsubstituted C3 to C15 alkyl.

[0015] The organometallic compound may include substituted or unsubstituted cyclopentadiene-based ligands, substituted or unsubstituted β-diketone-based ligands, substituted or unsubstituted ketoiminate-based ligands, substituted or unsubstituted pyrrole-based ligands, substituted or unsubstituted imidazole-based ligands, substituted or unsubstituted amidino-based ligands, substituted or unsubstituted alkoxide-based ligands, substituted or unsubstituted amide-based ligands, or combinations thereof.

[0016] The organometallic compound can be represented by Chemical Formula 2.

[0017] [Chemical formula 2]

[0018] M(A)2

[0019] In Chemical Formula 2, M is Sr or Ba, and A is derived from the compound represented by Chemical Formula 3,

[0020] [Chemical formula 3]

[0021]

[0022] In chemical formula 3, R a to R e are independently hydrogen or substituted or unsubstituted C1 to C30 alkyl.

[0023] R a to R e At least one of the may be a substituted or unsubstituted C3 to C30 branched chain alkyl group.

[0024] In Chemical Formula 1, R 1 to R 3 Can be the same.

[0025] R 1 to R 3 and may independently be substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl or substituted or unsubstituted decyl.

[0026] The compound containing an unshared electron pair may be included in an amount of about 10 wt % to about 90 wt % based on the total weight of the composition for depositing a thin film.

[0027] Organometallic compounds (m 1 ) and compounds containing unshared electron pairs (m 2 ) equivalent ratio (m 2 / m 1 ) can be from about 0.1 to about 5.

[0028] When measured using thermogravimetric analysis at 1 atmosphere under an argon (Ar) atmosphere, the difference between the temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing a non-shared electron pair may be less than or equal to about 90°C.

[0029] When thermogravimetric analysis is measured under an argon (Ar) atmosphere at 1 atm, the temperature at which a 50% weight loss occurs relative to the initial weight of the composition for depositing a thin film may be lower than the temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing an unshared electron pair.

[0030] The composition used to deposit the thin film can have a viscosity of less than or equal to about 500 centipoise.

[0031] The aforementioned composition for depositing a thin film may be a composition for depositing a first thin film.

[0032] According to another embodiment, a method of manufacturing a thin film includes vaporizing a composition for depositing a first thin film and depositing the vaporized composition for depositing the first thin film on a substrate.

[0033] The method for manufacturing a thin film may further include vaporizing a composition for depositing a second thin film and depositing the vaporized composition for depositing a second thin film on a substrate, wherein the composition for depositing the second thin film may include a second organic metal compound, and the second organic metal compound includes titanium, zirconium, hafnium, niobium, tantalum or a combination thereof.

[0034] The vaporized composition for depositing the first thin film and the vaporized composition for depositing the second thin film may be deposited on the substrate together or independently of each other.

[0035] The vaporized composition for depositing the first thin film and the vaporized composition for depositing the second thin film may be deposited on the substrate together or alternately.

[0036] The vaporizing of the composition for depositing the first thin film may include heating the composition for depositing the first thin film at a temperature of less than or equal to about 300°C.

[0037] The deposition of the vaporized composition for depositing the first thin film on the substrate may further include reacting the vaporized composition for depositing the first thin film with a reactive gas, and

[0038] The reaction gas may include water vapor (H2O), oxygen (O2), ozone (O3), plasma, hydrogen peroxide (H2O2), ammonia (NH3), hydrazine (N2H4), or a combination thereof.

[0039] The deposition of the vaporized composition for depositing the first thin film on the substrate may be performed using an atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) method.

[0040] According to another embodiment, a thin film manufactured using the composition for depositing a thin film according to an embodiment is provided.

[0041] According to another embodiment, a semiconductor device including the thin film according to an embodiment is provided.

[0042] The composition for depositing a thin film can improve viscosity and volatility, and a thin film manufactured from the composition for depositing a thin film can provide a semiconductor device having high reliability in electrical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is a graph showing the viscosity of the composition for depositing a thin film corresponding to the contents of the organometallic compound of Chemical Formula 2-1, triheptylamine, and trioctylamine in the composition for depositing a thin film according to Examples 1-1 to 1-7, Examples 2-1 to 2-7, and Comparative Example 1.

[0044] Figure 2 : is a graph showing weight change rates corresponding to temperatures of the compositions for depositing a thin film according to Examples 1-4, Examples 2-4, and Comparative Examples 2-4.

[0045] Figure 3 is a graph showing the weight change rate of the composition for depositing a thin film at 500° C. over time according to Examples 1-4, Examples 2-4, Comparative Example 1, and Comparative Examples 2-4. DETAILED DESCRIPTION

[0046] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the embodiments of the present invention. However, the present disclosure can be implemented in many different forms and should not be construed as being limited to the example embodiments set forth herein.

[0047] Hereinafter, unless otherwise stated, in the specification, when a part such as a layer, a film, a thin film, a region, a plate, etc. is referred to as being “on” another part, it not only includes the case where the other part is “close to” the other part, but also includes the case where the other part exists in between.

[0048] Hereinafter, as used herein, when no definition is otherwise provided, "a combination thereof" means a mixture of components, a composite, a coordination compound, a laminate, an alloy, and the like.

[0049] Hereinafter, as used herein, when no definition is otherwise provided, "substituted" refers to replacement of a hydrogen atom with deuterium, halogen, hydroxyl, cyano, nitro, -NRR' (wherein R and R' are 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 independently hydrogen, substituted or unsubstituted C1 to C30 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C30 saturated or unsaturated alicyclic hydrocarbon group, or substituted or unsubstituted C6 to C30 aromatic hydrocarbon group), C1 to C20 alkyl group, C1 to C10 haloalkyl group, C1 to C10 alkylsilanyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, or a combination thereof. "Unsubstituted" means that the hydrogen atom remains without being replaced by another substituent.

[0050] As used herein, when no definition is otherwise provided, "hetero" means that a functional group contains 1 to 3 heteroatoms selected from N, O, S and P, and the rest are carbon.

[0051] As used herein, when no definition is otherwise provided, "alkyl" refers to a straight chain aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" without any double or triple bonds. 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 group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

[0052] As used herein, unless otherwise defined, "saturated aliphatic hydrocarbon group" refers to a hydrocarbon group in which the bonds between carbon atoms in the molecule are formed by single bonds. The saturated aliphatic hydrocarbon group can be a C1 to C20 saturated aliphatic hydrocarbon group. For example, the saturated aliphatic hydrocarbon group can 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 can be a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2,2-dimethylpropyl or tert-butyl group.

[0053] As used herein, "amine group" refers to a primary amine group, a secondary amine group, or a tertiary amine group.

[0054] As used herein, “silylamine” refers to a primary, secondary or tertiary amine group, in which the nitrogen atom is substituted with one or more silyl groups, and the hydrogen atoms in the silyl group may be replaced with halogen (—F, —Cl, —Br or —I) or a substituted or unsubstituted C1 to C20 alkyl group.

[0055] As used herein, “organometallic compound” refers to a compound including a chemical bond between a metal element and a carbon, oxygen or nitrogen element, wherein the chemical bond refers to a covalent bond, an ionic bond and a coordination bond.

[0056] As used herein, "ligand" refers to a molecule or ion that chemically bonds around a metal ion, and the molecule may be an organic molecule, wherein the chemical bond refers to a covalent bond, an ionic bond, and a coordination bond.

[0057] As used herein, viscosity is based on measurement under the following measurement conditions.

[0058] [Viscosity measurement conditions]

[0059] Viscometer: RVDV-II (BROOKFIELD Company)

[0060] Rotor number: CPA-40Z

[0061] Torque / rpm: 20% to 80% torque / 1 rpm to 100 rpm

[0062] ·Measurement temperature (sample cup temperature): 25℃

[0063] In order to manufacture a thin film with high dielectric constant and high capacitance using a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process, an organometallic compound containing an alkaline earth metal is used. Alkaline earth metals refer to Group II elements, for example, and may contain strontium, barium, or a combination thereof. However, since the organometallic compound is mainly solid or has a low vapor pressure, it is difficult to form the thin film uniformly in a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. Therefore, a composition for depositing a thin film that is thermally stable and easily vaporized and has a high dielectric constant and high capacitance has been required.

[0064] According to one embodiment, a composition for depositing a thin film includes: an organic metal compound including strontium, barium or a combination thereof; and at least one compound represented by Chemical Formula 1 containing an unshared electron pair.

[0065] [Chemical formula 1]

[0066] R 1 R 2 R 3 N

[0067] In Chemical Formula 1, R 1 to R 3 are independently substituted or unsubstituted C3 to C15 alkyl.

[0068] For example, the organometallic compound can include one or more monovalent ligands, one or more divalent ligands, or a combination thereof.

[0069] For example, the organometallic compound may include two or more ligands, and may include, for example, two or three ligands.

[0070] For example, the organometallic compound may include substituted or unsubstituted cyclopentadiene-type ligands, substituted or unsubstituted β-diketone-type ligands, substituted or unsubstituted ketimine-type ligands, substituted or unsubstituted pyrrole-type ligands, substituted or unsubstituted imidazole-type ligands, substituted or unsubstituted amidine-type ligands, substituted or unsubstituted alkoxide-type ligands, substituted or unsubstituted amide-type ligands, or combinations thereof.

[0071] For example, the organometallic compound may be represented by Chemical Formula 2.

[0072] [Chemical formula 2]

[0073] M(A)2

[0074] In Chemical Formula 2, M is an alkaline earth metal, and A is a substituted or unsubstituted cyclopentadiene ligand, a substituted or unsubstituted β-diketone ligand, a substituted or unsubstituted ketimine ligand, a substituted or unsubstituted pyrrole ligand, a substituted or unsubstituted imidazole ligand, a substituted or unsubstituted amidine ligand, a substituted or unsubstituted alkoxide ligand, a substituted or unsubstituted amide ligand, or a combination thereof.

[0075] For example, M can be strontium, barium, or a combination thereof.

[0076] For example, A may be derived from a compound represented by Chemical Formula 3,

[0077] [Chemical formula 3]

[0078]

[0079] In chemical formula 3, R a to R e are independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0080] Without being bound by any particular theory, in the organometallic compound represented by Chemical Formula 2, the organometallic M may be single-bonded to any one of the carbon atoms constituting the two pentagonal rings of the compound represented by Chemical Formula 3, or may each be bonded to a delocalized electron pair in the five carbon atoms constituting the two pentagonal rings of the compound represented by Chemical Formula 3.

[0081] The substituted or unsubstituted C1 to C20 alkyl group may be, for example, a substituted or unsubstituted C1 to C15 alkyl group, for example, a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C1 to C6 alkyl group, for example, a substituted or unsubstituted C1 to C4 alkyl group, or a combination thereof. Specifically, the substituted or unsubstituted C1 to C20 alkyl group may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted heptyl group, a substituted or unsubstituted octyl group, a substituted or unsubstituted nonyl group, a substituted or unsubstituted decyl group, or a combination thereof, but is not limited thereto.

[0082] For example, the substituted or unsubstituted C1 to C20 alkyl group may include a substituted or unsubstituted C1 to C20 straight chain alkyl group, a substituted or unsubstituted C3 to C20 branched chain alkyl group, or a combination thereof.

[0083] The C1 to C20 straight-chain alkyl group may be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted n-pentyl group, a substituted or unsubstituted n-hexyl group, a substituted or unsubstituted n-heptyl group, a substituted or unsubstituted n-octyl group, or a combination thereof.

[0084] In addition, the substituted or unsubstituted branched C3 to C20 alkyl group may be a substituted or unsubstituted C3 to C20 isoalkyl group, a substituted or unsubstituted C3 to C20 secondary alkyl group, a substituted or unsubstituted C4 to C20 tertiary alkyl group, or a substituted or unsubstituted C5 to C20 neoalkyl group. Specifically, the substituted or unsubstituted C3 to C20 branched alkyl group may be a substituted or unsubstituted isopropyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted secondary butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted isopentyl group, a substituted or unsubstituted secondary pentyl group, a substituted or unsubstituted tert-pentyl group, or a substituted or unsubstituted neopentyl group, and is desirably a substituted or unsubstituted isopropyl group, a substituted or unsubstituted secondary butyl group, or a combination thereof.

[0085] For example, R a to R eAt least one of them may independently be a substituted or unsubstituted C1 to C20 alkyl group, R a to R e At least two of them may independently be substituted or unsubstituted C1 to C20 alkyl groups, and R a to R e 2 to 4 of the groups may independently be substituted or unsubstituted C1 to C20 alkyl groups. Herein, the substituted or unsubstituted C1 to C20 alkyl group is the same as described above.

[0086] For example, R a to R e At least one of them may be independently a substituted or unsubstituted C3 to C20 branched alkyl group, R a to R e At least two of them may independently be substituted or unsubstituted C3 to C20 branched chain alkyl groups, and R a to R e 2 or 3 of them may independently be substituted or unsubstituted C3 to C20 branched chain alkyl groups. Herein, the substituted or unsubstituted C3 to C20 branched chain alkyl groups are the same as described above.

[0087] For example, R b , R c and R e and C3 to C20 branched chain alkyl groups.

[0088] For example, R b , R c and R e The groups may independently be substituted or unsubstituted C3 to C20 isoalkyl groups, substituted or unsubstituted C3 to C20 secondary alkyl groups, or combinations thereof.

[0089] For example, R b , R c and R e It may independently be substituted or unsubstituted isopropyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, or a combination thereof.

[0090] For example, R a to R e At least one of may be hydrogen, and for example, R a and R d It may be hydrogen.

[0091] For example, R b With R e Can be the same or different.

[0092] For example, two A's from Formula 3 may be the same or different, but the two A's may be the same. Specifically, in Formula 3, R a May be the same or different, but may ideally be the same; R b May be the same or different, but may ideally be the same; R c May be the same or different, but may ideally be the same; R d may be the same or different, but are desirably the same; and R e They may be the same or different, but ideally are the same.

[0093] For example, the organometallic compound represented by Chemical Formula 2 may be Sr(iPr3Cp)2, Sr(tertBu3Cp)2, Sr(secBu3Cp)2, Sr(Me5Cp)2, Sr(Me4,EtCp)2, Sr(Me4,nPrCp)2, Sr(Me4,nBuCp)2, Sr(iPr2,secBuCp)2, Sr(iPr2,Et2Cp)2, Sr(iBu,secBu2Cp)2, or a combination thereof. Herein, Cp means a group derived from cyclopentadiene, i means iso, sec means secondary, tert means tertiary, n means normal, Me means methyl, Et means ethyl, Pr means propyl, and Bu means butyl, respectively.

[0094] The composition for depositing a thin film may include one or two or more of the aforementioned organometallic compounds, and specifically, may include one or two or more types of the organometallic compound represented by Chemical Formula 2.

[0095] For example, the content of the organometallic compound may be about 10 wt % to about 90 wt %, such as about 15 wt % to about 80 wt %, about 20 wt % to about 70 wt %, or about 25 wt % to about 60 wt %, based on the total weight of the composition for depositing a thin film.

[0096] The organometallic compound containing an alkaline earth metal may be a solid or a liquid at room temperature (e.g., about 20±5° C., about 1 atm), and most of the organometallic compounds containing an alkaline earth metal exhibit a high dielectric constant, but have a high viscosity and low volatility. For example, the organometallic compound may be a solid at room temperature (e.g., about 20±5° C., about 1 atm), or may be a liquid having a viscosity of about 500 centipoise or more and / or low volatility. However, the aforementioned composition for depositing a thin film also includes a compound containing an unshared electron pair, and thus may be a liquid exhibiting low viscosity and high volatility at room temperature (e.g., about 20±5° C., about 1 atm). Therefore, the composition for depositing a thin film may be easily transported through a fluid channel (Liquid Delivery System, LDS process), and the composition for depositing a thin film may be easily vaporized and deposited at a relatively low temperature.

[0097] For example, as described above, the compound containing an unshared electron pair can be represented by Chemical Formula 1. In Chemical Formula 1, R 1 to R 3 Can be the same or different, but R 1 to R 3 Ideally the same.

[0098] For example, R 1 to R 3 It may independently be a substituted or unsubstituted C4 to C13 alkyl group, such as a substituted or unsubstituted C4 to C10 alkyl group, such as a substituted or unsubstituted C4 to C8 alkyl group, such as a substituted or unsubstituted C5 to C13 alkyl group, such as a substituted or unsubstituted C6 to C13 alkyl group, such as a substituted or unsubstituted C7 to C13 alkyl group, such as a substituted or unsubstituted C7 to C8 alkyl group, or a combination thereof.

[0099] For example, R 1 to R 3 and may independently be substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl or substituted or unsubstituted decyl.

[0100] For example, the compound containing an unshared electron pair may be tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, or a combination thereof.

[0101] For example, the compound containing an unshared electron pair can be a liquid at room temperature (e.g., about 20±5°C, about 1 atmosphere), and the viscosity of the liquid compound containing an unshared electron pair can be different from the viscosity of the organometallic compound, and the viscosity of the liquid compound containing an unshared electron pair can ideally be less than the viscosity of the organometallic compound.

[0102] For example, the compound containing an unshared electron pair can have a viscosity of less than or equal to about 100 centipoise, such as about 1 centipoise to about 75 centipoise, about 1 centipoise to about 50 centipoise, or about 1 centipoise to about 25 centipoise.

[0103] For example, when thermogravimetric analysis is measured under an argon (Ar) atmosphere at 1 atmosphere, the temperature at which a 50% weight loss relative to the initial weight of the compound containing an unshared electron pair occurs may be greater than or equal to about 150°C, for example, from about 150°C to about 400°C, from about 175°C to about 350°C, or from about 200°C to about 300°C.

[0104] The composition for depositing a thin film may include one or more types of the aforementioned compounds containing unshared electron pairs, and specifically, may include one or more types of the aforementioned compounds containing unshared electron pairs represented by Chemical Formula 1.

[0105] For example, the content of the compound containing an unshared electron pair may be about 10 wt % to about 90 wt %, such as about 15 wt % to about 80 wt %, about 20 wt % to about 70 wt %, or about 25 wt % to about 60 wt %, based on the total weight of the composition for depositing a thin film. Therefore, the composition for depositing a thin film can be easily transported through a fluid channel (liquid delivery system, LDS process).

[0106] Organometallic compounds (m 1 ) and compounds containing unshared electron pairs (m 2 ) equivalent ratio (m 2 / m 1 ) may be about 0.1 to about 5, for example, about 0.25 to about 4, about 0.4 to about 3, or about 0.5 to about 2. Therefore, the composition for depositing a thin film can be easily transported through a fluid channel (liquid delivery system, LDS process).

[0107] When thermogravimetric analysis is measured under an argon (Ar) atmosphere at 1 atmosphere, the difference between the temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing a non-shared electron pair may be less than or equal to about 90°C, for example, from about 0°C to about 90°C, from about 0°C to about 70°C, or from about 0°C to about 60°C.

[0108] Therefore, when the composition for depositing a thin film is vaporized, one of the organic metal compound and the compound containing an unshared electron pair is vaporized first, and then the other is not vaporized (2-step vaporization), but vaporized together (1-step vaporization) so that the composition for depositing a thin film is uniformly deposited.

[0109] For example, when thermogravimetric analysis is measured under an argon (Ar) atmosphere at 1 atm, the temperature at which a 50% weight loss occurs relative to the initial weight of the composition for depositing a thin film may be lower than the temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing a non-shared electron pair. That is, the volatility of the composition for depositing a thin film may be higher than the volatility of each of the organometallic compound and the compound containing a non-shared electron pair included in the composition for depositing a thin film. Therefore, the composition for depositing a thin film may be easily vaporized and deposited at a relatively low temperature, and a uniform thin film may be formed.

[0110] For example, the viscosity of the composition for depositing a thin film can be less than or equal to about 500 centipoise, such as less than or equal to about 300 centipoise, less than or equal to about 200 centipoise, less than or equal to about 100 centipoise, or less than or equal to about 50 centipoise, such as about 1 centipoise to about 300 centipoise, about 1 centipoise to about 200 centipoise, about 1 centipoise to about 100 centipoise, or about 1 centipoise to about 50 centipoise. Therefore, the composition for depositing a thin film can be easily transported through a fluid channel (liquid delivery system, LDS process).

[0111] The aforementioned composition for depositing a thin film may further contain other compounds in addition to the aforementioned organometallic compound and the compound containing an unshared electron pair.

[0112] The aforementioned composition for depositing a thin film may be a composition for depositing a first thin film.

[0113] According to another embodiment, a method of manufacturing a thin film includes vaporizing a composition for depositing a first thin film and depositing the vaporized composition for depositing the first thin film on a substrate.

[0114] For example, gasifying the composition for depositing the first thin film may include providing the composition for depositing the first thin film to the first reactor, and providing the composition for depositing the first thin film to the first reactor may be providing the composition for depositing the first thin film to the first reactor through a fluid channel.

[0115] For example, vaporizing the composition for depositing the first thin film may include heating the composition for depositing the first thin film at a temperature less than or equal to about 300°C, for example, heating the composition for depositing the first thin film at a temperature of about 50°C to about 300°C, about 50°C to about 250°C, or about 50°C to about 200°C.

[0116] For example, the method of manufacturing a thin film may further include vaporizing the composition for depositing the second thin film and depositing the vaporized composition for depositing the second thin film on a substrate.

[0117] The composition for depositing the second thin film may include a second organic metal compound, which includes titanium, zirconium, hafnium, niobium, tantalum or a combination thereof, and the second organic metal compound may include substituted or unsubstituted cyclopentadiene-type ligands, substituted or unsubstituted β-diketone-type ligands, substituted or unsubstituted ketimine-type ligands, substituted or unsubstituted pyrrole-type ligands, substituted or unsubstituted imidazole-type ligands, substituted or unsubstituted amidine-type ligands, substituted or unsubstituted alkoxide-type ligands, substituted or unsubstituted amide-type ligands or a combination thereof.

[0118] In addition to the second organometallic compound, the composition for depositing the second film may or may not further include a solvent, and when the solvent is not further included, the second organometallic compound may be in a liquid state at room temperature (e.g., about 20±5°C, about 1 atmosphere). When the composition for depositing the second film further includes a solvent, the solvent may be an organic solvent, such as a polar solvent, such as diethyl ether, petroleum ether, tetrahydrofuran or 1,2-dimethoxyethane. When an organic solvent is included, an organic solvent having a molar ratio of 2 times that of the organometallic compound may be included. Thus, the organometallic compound included in the composition for depositing the film may be coordinated by the organic solvent to improve the stability of the organometallic compound. Therefore, it is possible to inhibit the formation of oligomers formed by reacting the central metal atom contained in the organometallic compound with other organometallic compounds around it. In addition, the composition for depositing a film comprising an organic solvent may further increase the vapor pressure of the organometallic compound present in the form of a single molecule.

[0119] For example, vaporizing the composition for depositing the second thin film may include providing (via a fluid channel) the composition for depositing the second thin film to the first reactor or a second reactor different from the first reactor.

[0120] For example, vaporizing the composition for depositing the second thin film may include heating the composition for depositing the second thin film at a temperature less than or equal to about 200° C., for example, heating the composition for depositing the second thin film at a temperature of about 30° C. to about 200° C., about 30° C. to about 175° C., or about 30° C. to about 150° C.

[0121] For example, the composition for depositing the first thin film and the composition for depositing the second thin film may be vaporized together or independently. When the composition for depositing the first thin film and the composition for depositing the second thin film are each independently vaporized, the vaporized composition for depositing the first thin film and the vaporized composition for depositing the second thin film may be deposited on the substrate together or independently, and they may be deposited, for example, alternately.

[0122] For example, deposition of the vaporized composition for depositing a first thin film on a substrate may further include reacting the vaporized composition for depositing the first thin film with a reaction gas, and deposition of the vaporized composition for depositing a second thin film on a substrate may further include reacting the vaporized composition for depositing the second thin film with a reaction gas.

[0123] For example, the reactive gas may be an oxidant such as water vapor (H2O), oxygen (O2), ozone (O3), plasma, hydrogen peroxide (H2O2), ammonia (NH3), hydrazine (N2H4), or a combination thereof.

[0124] The deposition method is not particularly limited, but the method of manufacturing the thin film described above can be performed using an atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) method. Specifically, the deposition of the vaporized composition for depositing the first thin film and / or the vaporized composition for depositing the second thin film on the substrate can be performed using an atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) method.

[0125] For example, the deposition of the vaporized composition for depositing the first thin film and / or the vaporized composition for depositing the second thin film on the substrate may be performed at a temperature of about 100°C to about 1000°C.

[0126] According to another embodiment, a thin film manufactured using the composition for depositing a thin film according to an embodiment is provided. The thin film may be a thin film manufactured by the method for manufacturing a thin film according to an embodiment.

[0127] For example, the film may be a perovskite film, for example, the film may include strontium titanium oxide, barium strontium titanium oxide, rubidium strontium oxide, cerium strontium oxide, or a combination thereof. Specifically, the film may include SrTiO3, Ba x Sr 1-x TiO3 (wherein x is 0.1 to 0.9), SrRuO3, SrCeO3 or a combination thereof.

[0128] For example, the thickness of the thin film may be less than about 10 nanometers, and the dielectric constant value of the thin film may be greater than or equal to about 50. Therefore, the thin film may have a uniform thickness and excellent leakage current characteristics while forming a fine pattern.

[0129] The thin film may be a uniform thin film exhibiting high dielectric constant and high capacitance as well as excellent insulating properties. Therefore, the thin film may be an insulating layer, and the insulating layer may be included in an electrical device and an electronic device. The electrical device and the electronic device may be a semiconductor device, and the semiconductor device may be, for example, a dynamic random-access memory (DRAM).

[0130] According to another embodiment, a semiconductor device including the thin film according to an embodiment is provided. Since the semiconductor device includes the thin film according to an embodiment, electrical characteristics and reliability can be improved.

[0131] Hereinafter, the embodiments are described in more detail with reference to examples. However, these examples are exemplary, and the scope of the claims is not limited thereto.

[0132] Preparation of compositions for depositing thin films

[0133] Examples 1-1 to 1-7 and Comparative Example 1

[0134] The compositions for depositing thin films (liquid at room temperature) were respectively prepared to have the compositions shown in Table 1 by mixing the organometallic compound of Chemical Formula 2-1 (SR8820, Ereztech LLC.; TGA 50 wt% weight loss temperature = 265°C, solid at room temperature) and triheptylamine (I0361, Tokyo Chemical Industry (TCI); TGA 50 wt% weight loss temperature = 243°C, liquid at room temperature), and then stirring the mixture.

[0135] [Chemical formula 2-1]

[0136] Sr A2 (where A is )

[0137] [Table 1]

[0138]

[0139] Example 2-1 to Example 2-7

[0140] Compositions for depositing thin films (liquid at room temperature) were respectively prepared to have the compositions shown in Table 2 by mixing the organometallic compound of Chemical Formula 2-1 with trioctylamine (I0362, Tokyo Chemical Industry (TCI); TGA 50 wt% weight loss temperature = 269°C, liquid at room temperature), and then stirring the mixture.

[0141] [Table 2]

[0142]

[0143] Comparative Examples 2-1 to 2-7

[0144] Compositions for depositing thin films (liquid at room temperature) were prepared to have the compositions shown in Table 3, respectively, by mixing the organometallic compound of Chemical Formula 2-1 with triethylamine (I0424, Tokyo Chemical Industry (TCI); TGA 50 wt% weight loss temperature = 40.4°C, liquid at room temperature), and then stirring the mixture.

[0145] [Table 3]

[0146]

[0147] Evaluation 1

[0148] The compositions for depositing thin films according to Examples and Comparative Examples were measured with respect to viscosity under the following conditions, and the results are shown in Tables 1 to 3 and Figure 1 middle.

[0149] [Viscosity measurement conditions]

[0150] Viscometer: RVDV-II (Brownfield)

[0151] Rotor number: CPA-40Z

[0152] Torque / rpm: 20% to 80% torque / 1 rpm to 100 rpm

[0153] ·Measurement temperature (sample cup temperature): 25℃

[0154] Refer to Tables 1 to 3 and Figure 1 , the compositions for depositing thin films according to Examples 1-1 to 2-7 and Comparative Example 1 have a viscosity low enough to be delivered through a fluid channel (liquid delivery system).

[0155] Evaluation 2

[0156] The compositions for depositing thin films according to the examples and comparative examples were evaluated in a thermogravimetric analysis (TGA) method under argon (Ar) gas and 1 atm. (Measuring equipment: TG209F3, Netzsch- GmbH)

[0157] 20±2 mg of the compositions for depositing thin films according to Examples and Comparative Examples were respectively obtained and then placed in an alumina sample container, and the weight change rate thereof was measured while heating each composition for depositing a thin film to 500° C. at 10° C. / min.

[0158] In addition, 20±2 mg of the compositions for depositing thin films according to Examples and Comparative Examples were respectively obtained and then placed in an alumina sample container, and their weight change rate over time was measured while each composition for depositing a thin film was maintained at 500°C.

[0159] The weight change rate is a value calculated using calculation equation 1.

[0160] [Calculation equation 1]

[0161] Weight change rate (%) = (weight after heat treatment / initial weight) × 100%

[0162] The weight change rates of the compositions for depositing thin films according to the Examples and Comparative Examples are shown in Figure 2 The weight change rates of the compositions for depositing thin films according to the examples and comparative examples at 500° C. over time are shown in Tables 1 to 3 and Figure 3 middle.

[0163] refer to Figure 2 , the composition for depositing a thin film according to Examples 1-4 and Examples 2-4 exhibits a 50% weight loss relative to each initial weight at a temperature lower than the temperature at which each organometallic compound and each compound containing a non-shared electron pair included in the composition for depositing a thin film exhibits a 50% weight loss relative to each initial weight.

[0164] In addition, refer to Tables 1 to 3 and Figure 2 and Figure 3 , the composition for depositing a thin film according to the example exhibits a single-step volatilization behavior (single-step vaporization), but the compositions of Comparative Examples 2-1 to 2-7 exhibit a double volatilization behavior (two-step vaporization), in which either one of the organic metal compound and the non-shared electron pair contained in each composition for depositing a thin film volatilizes, and then the other volatilizes.

[0165] In addition, Figure 3 Since the compositions for depositing a thin film according to Examples 1-4 and Examples 2-4 exhibited a greater absolute value of the slope than that of Comparative Example 1, the compositions for depositing a thin film comprising the organometallic compound and the compound containing a non-shared electron pair of Chemical Formula 1 according to the examples exhibited excellent volatility compared to the composition for depositing a thin film comprising only the organometallic compound.

[0166] In summary, refer to Tables 1 to 3 and Figures 1 to 3 , the composition for depositing a thin film according to an embodiment of the present invention is more suitable for depositing a uniform thin film.

[0167] Manufacturing thin films

[0168] 200 g of the compositions for depositing a thin film according to Examples 1-1 to 2-7 were respectively loaded in a bubbler type 300 cubic centimeter (cc) tank and formed into a thin film by using an ALD apparatus.

[0169] In order to supply enough composition for depositing thin film, the tank is heated to 50°C to 150°C, and in order to prevent the composition for depositing thin film from condensing in the pipe, the pipe is heated to 10°C higher than the tank. Herein, Ar gas with high purity (99.999%) is used as a carrier gas, and when Ar gas is flowed at 50 standard cubic centimeters per minute (sccm) to 500 standard cubic centimeters per minute, the composition for depositing thin film is supplied. Subsequently, for the oxidant reaction gas, ozone gas is flowed at 100 standard cubic centimeters per minute to 500 standard cubic centimeters per minute, and when the temperature of the silicon substrate becomes 200°C to 450°C, the thin films are respectively deposited on the silicon substrate. The deposited thin film is heat-treated at 650°C for several minutes by using a rapid thermal annealing (RTA) device.

[0170] The films exhibited a growth per cycle (GPC) of 1.06±0.02 Å / cycle and a thickness uniformity of 5.0±0.5% depending on the deposition cycle, and a crystalline phase was observed in the films grown at 340° C. or higher.

[0171] In the above, certain exemplary embodiments of the present invention have been described and illustrated, however, it is obvious to those skilled in the art that the present invention is not limited to the exemplary embodiments as described, and various modifications and conversions may be made without departing from the spirit and scope of the present invention. Therefore, the modified or converted exemplary embodiments may not be understood solely from the technical concepts and aspects of the present invention, and the modified exemplary embodiments are within the scope of the claims of the present invention.

Claims

1. A composition for depositing a thin film, comprising: An organometallic compound comprising strontium, barium, or a combination thereof; as well as At least one compound having an unshared electron pair represented by Chemical Formula 1: [Chemical formula 1] R 1 R 2 R 3 N Wherein, in Chemical Formula 1, R 1 to R 3 are independently substituted or unsubstituted C3 to C15 alkyl, The composition for depositing a thin film has a viscosity less than or equal to 500 centipoise, measured according to the following conditions: Torque / rpm: 20% to 80% torque / 1 rpm to 100 rpm Sample cup temperature: 25°C.

2. The composition for depositing a thin film according to claim 1, wherein the organometallic compound comprises a substituted or unsubstituted cyclopentadiene-type ligand, a substituted or unsubstituted β-diketone-type ligand, a substituted or unsubstituted ketimine-type ligand, a substituted or unsubstituted pyrrole-type ligand, a substituted or unsubstituted imidazole-type ligand, a substituted or unsubstituted amidine-type ligand, a substituted or unsubstituted alkoxide-type ligand, a substituted or unsubstituted amide-type ligand, or a combination thereof.

3. The composition for depositing a thin film according to claim 1, wherein the organic metal compound is represented by Chemical Formula 2: [Chemical formula 2] M(A)2 in, In chemical formula 2, M is strontium or barium, and A is derived from a compound represented by Chemical Formula 3, [Chemical formula 3] Wherein, in Chemical Formula 3, R a to R e are independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

4. The composition for depositing a thin film according to claim 3, wherein R a to R e At least one of the groups is a substituted or unsubstituted C3 to C30 branched chain alkyl group.

5. The composition for depositing a thin film according to claim 1, wherein in Chemical Formula 1, R 1 to R 3 same.

6. The composition for depositing a thin film according to claim 1, wherein R 1 to R 3 is substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl or substituted or unsubstituted decyl. 7 . The composition for depositing a thin film according to claim 1 , wherein the content of the compound containing an unshared electron pair is 10 wt % to 90 wt % based on the total weight of the composition for depositing a thin film. 8 . The composition for depositing a thin film according to claim 1 , wherein an equivalent ratio of the number of moles of the compound containing an unshared electron pair to the number of moles of the organometallic compound is 0.1 to 5.

9. The composition for depositing a thin film according to claim 1, wherein the difference between the temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing a non-shared electron pair occurs, when measured using thermogravimetric analysis at 1 atm under an argon atmosphere, is less than or equal to 90°C.

10. The composition for depositing a thin film according to claim 1, wherein when thermogravimetric analysis is measured under an argon atmosphere at 1 atm, the temperature at which 50% weight loss occurs relative to the initial weight of the composition for depositing a thin film is lower than The temperature at which a 50% weight loss occurs relative to the initial weight of the organometallic compound and the temperature at which a 50% weight loss occurs relative to the initial weight of the compound containing an unshared electron pair.

11. A method for manufacturing a thin film, comprising: vaporizing the composition for depositing the first thin film, and depositing the vaporized composition for depositing the first thin film on a substrate, The composition for depositing a first thin film comprises the composition for depositing a thin film as claimed in any one of claims 1 to 10.

12. The method for manufacturing a thin film according to claim 11, further comprising: vaporizing a composition for depositing a second thin film, and depositing the vaporized composition for depositing the second thin film on the substrate, The composition for depositing the second thin film includes a second organic metal compound, and the second organic metal compound includes titanium, zirconium, hafnium, niobium, tantalum or a combination thereof. 13 . The method for manufacturing a thin film according to claim 12 , wherein the vaporized composition for depositing the first thin film and the vaporized composition for depositing the second thin film are deposited on the substrate together or independently of each other. 14 . The method for manufacturing a thin film according to claim 11 , wherein the vaporizing of the composition for depositing the first thin film comprises heating the composition for depositing the first thin film at a temperature less than or equal to 300° C.

15. The method for producing a thin film according to claim 12, wherein The deposition of the vaporized composition for depositing the first thin film on the substrate further comprises reacting the vaporized composition for depositing the first thin film with a reaction gas, and The reaction gas includes water vapor, oxygen, ozone, plasma, hydrogen peroxide, ammonia, hydrazine or a combination thereof. 16 . The method for manufacturing a thin film according to claim 12 , wherein the depositing of the vaporized composition for depositing the first thin film on the substrate is performed using an atomic layer deposition or metal organic chemical vapor deposition method.

17. A thin film produced from the composition for depositing a thin film according to any one of claims 1 to 10.

18. A semiconductor device comprising the thin film according to claim 17.

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