KR20220157858A - Precursor for film deposition, deposition method of film and semiconductor device of the same - Google Patents

Abstract

The present invention relates to a precursor for forming a thin film containing a Group 4 transition metal and comprises an organometallic compound represented by Chemical Formula 1 below. In the chemical formula 1, M is Ti, Zr, or Hf; X is a hydrogen atom, a C_1-C_5 alkyl group, NR_4R_5, or OR_6; R_1 to R_6 may be the same as or different from each other, and each independently represents a hydrogen atom or a C_1-C_5 linear, branched or cyclic alkyl group; any one of R_1 may be an alkylamine group; and n is a natural number of 1, 2, or 3. Accordingly, a transition metal silicate thin film can be formed in a single process.

Description

A precursor for forming a thin film containing a Group 4 transition metal, a method for forming a thin film containing a Group 4 transition metal using the same, and a semiconductor device including the Group 4 transition metal-containing thin film. }

The present invention relates to a precursor for forming a group 4 transition metal-containing thin film, a method for forming a group 4 transition metal-containing thin film using the same, and a semiconductor device including the group 4 transition metal-containing thin film, and more particularly, atomic layer deposition (ALD). ) or a precursor capable of forming a thin film such as a group 4 transition metal-containing thin film, a transition metal silicate, a silicon-doped metal-containing thin film by containing a group 4 transition metal and silicon (Si) used in a chemical vapor deposition (CVD) process, A method of forming a thin film containing a Group 4 transition metal using the same and a semiconductor device including the thin film containing a Group 4 transition metal.

Various types of organometallic compounds have been developed and used as precursors for atomic layer deposition (ALD) or chemical vapor deposition (CVD) processes. These organometallic compounds require properties such as vaporization characteristics, gap between vaporization temperature and decomposition temperature, toxicity, chemical stability, thermal stability, ease of compound synthesis, and ease of thermal decomposition.

As one of these organometallic compounds, a precursor of an organometallic compound in the form of a complex compound containing a cyclopentadienyl group may be mentioned. It is known to be effective in forming

For example, in Korean Patent Registration No. 10-1263454, a crosslinked structure of alkylamine is formed between a cyclopentadienyl group such as Zr(CpCH ₂ CH ₂ NMe)(NMe ₂ ) ₂ and a zirconium atom, thereby providing thermal stability and step coating. It has excellent properties and exhibits excellent properties as a precursor that does not decompose even when stored at high temperatures for a long time.

In addition, Korean Patent Registration No. 10-1959519 discloses a technique of forming a transition metal silicate thin film by using an organometallic compound containing a metal atom and a silicon atom, and by adopting a crosslinked structure with high thermal stability, one precursor As a result, a transition metal silicate thin film can be formed.

In Korean Patent Publication No. 10-2019-0108281, the applicant uses an organometallic compound in which a crosslinked structure is formed between a central metal and a cyclopentadienyl group to provide a precursor that has excellent thermal stability and can solve problems occurring during the miniaturization process. have been developed

Based on this basic structure, it is expected to provide an effective precursor for ALD or CVD by developing a new precursor suitable for high-temperature deposition.

Republic of Korea Patent Registration No. 10-1263454 Republic of Korea Patent Registration No. 10-1959519 Republic of Korea Patent Publication No. 10-2019-0108281

The present invention has been made in view of the prior art as described above, and an object of the present invention is to provide a precursor for forming a Group 4 transition metal silicate (MSiO _x ) thin film that is excellent in thermal stability and suitable for high-temperature deposition.

In addition, it is an object of the present invention to provide a precursor for forming a thin film containing a Group 4 transition metal having increased stability through an organometallic compound having a cross-linked structure.

In addition, an object of the present invention is to provide a precursor capable of forming a transition metal silicate thin film by applying one organometallic compound containing a transition metal and a silicon atom as a precursor.

Another object of the present invention is to provide a method of forming a metal thin film containing a Group 4 transition metal using the precursor and a method of manufacturing a semiconductor device including the metal thin film containing a Group 4 transition metal.

The precursor for forming a metal thin film containing a Group 4 transition metal of the present invention to achieve the above object is characterized in that it comprises an organometallic compound represented by Formula 1 below.

[Formula 1]

In Formula 1, M is Ti, Zr, or Hf, X is a hydrogen atom, an alkyl group, NR ₄ R ₅ or OR ₆ , R ₁ to R ₆ may be the same as or different from each other, and each independently represents a hydrogen atom. Or a C ₁ -C ₅ straight-chain, branched or cyclic alkyl group, R ₁ may be an alkylamine group, and n is a natural number of 1, 2 or 3.

In addition, the precursor may additionally include a solvent, and the solvent may be any one or more of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines. have.

In addition, the solvent may be included in an amount of 1 to 99% by weight based on the total weight of the precursor for forming the Group 4 transition metal thin film.

The method of forming a thin film containing a Group 4 transition metal according to the present invention includes depositing a thin film containing a Group 4 transition metal on a substrate using the precursor for forming a thin film containing a Group 4 transition metal.

In this case, the group 4 transition metal-containing thin film may be deposited by atomic layer deposition or chemical vapor deposition.

In addition, a step of vaporizing the group 4 transition metal-containing thin film-forming precursor and transferring it into the chamber may be included.

In addition, the depositing may include positioning a substrate in a chamber, supplying the Group 4 transition metal-containing precursor composition for forming a thin film into the chamber, supplying a reactive gas or plasma of a reactive gas into the chamber, the It may include a step of treating by any one or more means of heat treatment, plasma treatment, and light irradiation in a chamber, and may be performed at 250 to 400 ° C.

The semiconductor device according to the present invention is characterized in that it includes a Group 4 transition metal-containing thin film manufactured by the method for forming a Group 4 transition metal-containing thin film.

Since the precursor according to the present invention has excellent thermal stability and is suitable for high-temperature deposition, it is suitable for forming a Group 4 transition metal-containing thin film, in particular, a Group 4 transition metal silicate (MSiO _x ) thin film.

In addition, thermal stability is increased through the cross-linked organometallic compound, and a transition metal silicate thin film can be formed in a single process by simultaneously containing a metal atom and a silicon atom in one compound.

In addition, it is possible to provide a method of forming a Group 4 transition metal-containing thin film and a method of manufacturing various semiconductor devices including the Group 4 transition metal-containing thin film by using the precursor.

1 is a conceptual diagram showing a thin film formation process using the precursor of the present invention.
Figure 2 is a graph measuring GPC change in the process of forming an HfSiOx thin film using the precursor of the present invention.
Figure 3 is a graph measuring the change in deposition rate according to the number of cycles in the process of forming an HfSiOx thin film using the precursor of the present invention.
4 is an XRD analysis result of a HfSiOx thin film formed by an ALD deposition process using the precursor of the present invention.

Hereinafter, the present invention will be described in more detail. Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The precursor for forming a thin film containing a Group 4 transition metal according to the present invention is characterized by including an organometallic compound represented by Formula 1 below.

[Formula 1]

In Formula 1, M is Ti, Zr, or Hf, X is a hydrogen atom, a C ₁ -C ₅ alkyl group, NR ₄ R ₅ or OR ₆ , R ₁ to R ₆ may be the same as or different from each other, , Each independently a hydrogen atom or a C ₁ -C ₅ straight-chain, branched or cyclic alkyl group, R ₁ may be any one of an alkylamine group, and n is a natural number of 1, 2 or 3.

Organometallic compounds as described above can be prepared through a conventional ligand synthesis method. That is, as shown in Schemes 1 to 3 below, it is prepared through a first step of reacting cyclopentane and an alkylamino compound, a second step of reacting the reaction product and an alkylsilicon compound, and a third step of reacting the reaction product and a zirconium compound. can do.

[Scheme 1]

[Scheme 2]

[Scheme 3]

The organometallic compound represented by Formula 1 may specifically include an organometallic compound selected from the following structures, but is not limited thereto.

The precursor of the present invention may additionally include a solvent. As the solvent, any one of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines, or mixtures thereof may be used. Examples of the C ₁ -C ₁₆ saturated or unsaturated hydrocarbon include toluene and heptane, and examples of the tertiary amine include dimethylethylamine.

In addition, when the solvent is included, it is preferably included in an amount of 1 to 99% by weight based on the total weight of the precursor for forming the metal film.

The precursor, which may or may not contain a solvent, may be vaporized, and a deposition process may be performed by supplying the precursor into the chamber. It is preferable to appropriately select and use a soluble solvent according to the nature of the organometallic compound. That is, when the organometallic compound exists in a liquid state at room temperature depending on the type, the deposition process may be performed without a separate solvent.

The method of forming a thin film containing a Group 4 transition metal of the present invention is characterized in that it comprises depositing a Group 4 transition metal-containing thin film on a substrate using the precursor for forming a Group 4 transition metal-containing thin film.

In this case, the Group 4 transition metal-containing precursor for thin film formation may additionally include a solvent as described above, and the solvent may be included in an amount of 1 to 99% by weight based on the total weight of the Group 4 transition metal-containing thin film formation precursor. have.

The manufacturing method of a Group 4 transition metal-containing thin film using a precursor containing an organometallic compound represented by Formula 1 is a metal thin film by conventional deposition except for using an organometallic compound represented by Formula 1 as a metal precursor. It may be performed according to a manufacturing method, and specifically, it may be performed by a method such as chemical vapor deposition (CVD) or atomic layer deposition (ALD).

That is, supplying the organometallic compound represented by Chemical Formula 1 onto the substrate for forming a metal thin film existing in the reactor, and supplying a reactive gas into the reactor, and 1 selected from the group consisting of heat treatment, plasma treatment, and light irradiation. It can be produced by a manufacturing method comprising the step of subjecting the species to a treatment process.

Referring to FIG. 1, the thin film formation process is described. First, the precursor of the present invention is introduced onto a substrate on which a reaction site is formed (FIG. 1(a)). The reactive group (X) bonded to the central metal atom of the organometallic compound represented by Formula 1 constituting the precursor is bonded to the reactive group on the surface of the substrate, wherein the reactive groups on the adjacent substrate surface are cross-linked to the central metal atom. Electron transfer occurs to the silicon atom of the silyl group, and at the same time electron transfer occurs from the silicon atom to another surface reactive group (FIG. 1(b)). Then, when a reactive gas is supplied, metal atoms and silicon atoms are simultaneously deposited on the surface of the substrate, and through this, a thin film of transition metal silicate (MSiO _x ) is formed.

As the substrate for forming the Group 4 transition metal-containing thin film, any substrate used in semiconductor manufacturing, which needs to be coated with a metal thin film due to technical action, can be used without particular limitation. Specifically, silicon substrate (Si), silica substrate (SiO ₂ ), silicon nitride substrate (SiN), silicon oxynitride substrate (SiON), titanium nitride substrate (TiN), tantalum nitride substrate (TaN), tungsten substrate (W) or a noble metal substrate, for example, a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh), or a gold substrate (Au) may be used.

The organometallic compound represented by Chemical Formula 1 may be transported through volatilized gas, a direct liquid injection method, or a liquid transport method in which the organometallic compound is dissolved in an organic solvent and transported may be used. The method of transferring the precursor to the volatilized gas is to put the container containing the precursor into a thermostat and bubble it with an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to evaporate the precursor, and then form a metal thin film. It can be carried out by transferring it onto a substrate, or by changing a liquid precursor into a vapor phase using a liquid delivery system (LDS) and then transferring it onto a substrate for forming a metal thin film.

In the case of the liquid transfer method in which the precursor is dissolved in an organic solvent and transported, as described above, it can be used in the form of a composition consisting of the organometallic compound represented by Formula 1 and a solvent. When it is difficult to vaporize sufficiently in a vaporizer of a liquid transfer type due to viscosity, the deposition process can be effectively performed by using it in the form of a composition containing a solvent.

Such a solvent should have properties capable of dissolving a solid material or a solvent capable of dissolving and dispersing a liquid material. In addition, considering the boiling point, density and vapor pressure conditions of the solvent, the viscosity reduction effect and the volatility improvement effect of the composition for forming a thin film are improved, and through this, the uniformity and step coverage characteristics of the deposited thin film are improved. It is desirable to select the solvent to allow for the formation of improved thin films.

In addition, when the organometallic compound represented by Chemical Formula 1 is supplied into the chamber, silicon (Si), titanium (Ti), A metal precursor containing at least one metal (M") selected from germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide atoms The second metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal. For example, when the metal is Si, the second metal precursor is SiH(N(CH ₃ ) ₂ ) ₃ , Si(N(C ₂ H ₅ ) ₂ ) ₄ , Si(N(C ₂ H ₅ )(CH ₃ )) ₄ , Si(N(CH ₃ ) ₂ ) ₄ , Si(OC ₄ H ₉ ) ₄ , Si(OC ₂ H ₅ ) ₄ , Si(OCH ₃ ) ₄ , Si(OC(CH ₃ ) ₃ ) ₄ and the like may be used.

The supply of the second metal precursor may be carried out in the same manner as the method of supplying the metal precursor of Chemical Formula 1, and the second metal precursor may be supplied together with the metal precursor of Chemical Formula 1 onto a substrate for forming a thin film, or a metal precursor. After completion of the supply of the precursor, it may be supplied sequentially.

The metal precursor of Formula 1 and optionally the second metal precursor as described above are preferably maintained at a temperature of 100 to 200° C. until supplied into the reaction chamber to bring them into contact with the substrate for forming the metal film, more preferably 130° C. It is good to maintain a temperature of 180 ° C.

In addition, after the step of supplying the metal precursor and before the supply of the reactive gas, the metal precursor of Chemical Formula 1 and optionally the second metal precursor are assisted in moving onto the substrate, or to have an appropriate pressure for deposition in the reactor, and also in the chamber A process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) in the reactor may be performed in order to discharge impurities present therein to the outside. At this time, it is preferable that the inert gas is purged so that the pressure in the reactor is 1 to 5 Torr.

After completion of the supply of the metal precursors, a reactive gas is supplied into the reactor, and one treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation is performed in the presence of the reactive gas.

The reactive gases include water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), hydrogen (H ₂ ), ammonia (NH ₃ ), nitrogen monoxide (NO), suboxides Any one of nitrogen (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and silane (SiH ₄ ) or a mixture thereof may be used. When carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a metal oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of metal alone or metal nitride may be formed. can

In addition, the heat treatment, plasma treatment, or light irradiation treatment process is to provide thermal energy for deposition of the metal precursor, and may be performed according to a conventional method. Preferably, in order to produce a metal thin film having a desired physical state and composition at a sufficient growth rate, the treatment process is performed such that the temperature of the substrate in the reactor is 100 to 1,000 ° C., preferably 300 to 500 ° C. .

In addition, in the treatment process, as described above, to help the movement of the reactive gas onto the substrate, to have an appropriate pressure for deposition in the reactor, and to release impurities or by-products present in the reactor to the outside, A process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) may be performed.

As described above, the input of the metal precursor, the input of the reactive gas, and the input of the inert gas are treated as one cycle. A metal-containing thin film can be formed by repeating one cycle or more.

Specifically, when an oxidizing gas is used as a reactive gas, a metal-containing thin film prepared may include a metal oxide represented by Chemical Formula 2 below.

[Formula 2]

(M _1-a M" _a ) O _b

In Formula 2, a is 0 ≤ a < 1, b is 0 < b ≤ 2, M is selected from the group consisting of Zr, Hf and Ti, M "is derived from a second metal precursor, silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide atoms.

In the manufacturing method of such a group 4 transition metal-containing thin film, by using a metal precursor having excellent thermal stability, the deposition process can be performed at a higher temperature than in the prior art during the deposition process, and particle contamination due to thermal decomposition of the precursor or impurities such as carbon A high-purity metal, metal oxide or metal nitride thin film can be formed without contamination. Accordingly, a thin film containing a Group 4 transition metal formed according to the manufacturing method of the present invention is useful as a high dielectric material film in a semiconductor device, particularly DRAM, CMOS, etc. in a semiconductor memory device.

As another embodiment, a Group 4 transition metal-containing thin film formed by the method of forming the Group 4 transition metal-containing thin film and a semiconductor device including the thin film are provided. For example, the semiconductor device may be a semiconductor device including a metal insulator metal (MIM) for a random access memory (RAM).

In addition, since the semiconductor device has the same configuration as a conventional semiconductor device except that the metal-containing thin film according to the present invention is included in a material film requiring high dielectric properties, such as DRAM, the configuration of the semiconductor device is described in this specification. A detailed description of is omitted.

The effects of the present invention will be described through examples below.

1. Synthesis of Intermediate A

Intermediate 3-(cyclopenta-2,4-dien-1-yl)propan-1-amine was synthesized through the following reaction pathway.

In a flame-dried 5,000 ml Schlenk flask, 308.5 g (5.710 mol, 2.5 equiv) of NaOMe and 376.9 g (5.710 mol, 2.5 equiv) of CpH were stirred in 3,200 ml THF under a nitrogen atmosphere for more than 12 hours to obtain a dark purple product. manufactured. The reacted product was stirred for 12 hours or longer in a nitrogen atmosphere in 500g (2.284mol, 1 equivalent) of 3-Bromopropylamine hydrobromide and 400㎖ Hexane to obtain a reactant. After obtaining a filtrate from the reactant through a filter, the solvent and volatile side reactants were removed under reduced pressure. Subsequently, the remaining dark purple liquid was distilled under reduced pressure to obtain 200 g (yield: 71%) of 3-(cyclopenta-2,4-dien-1-yl)propan-1-amine as a transparent liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ6.46~5.90, 2.78~2.66 (m, 4H, CpH), δ2.51~2.43 (m, 2H, - Characteristics of CH ₂ -), δ2.31~2.23(m, 2H, -CH ₂ -), δ1.55~1.39 (m, 2H, -CH ₂ -), δ0.46(s, 2H, NH ₂ ) By confirming the peak, it was confirmed that the target compound was synthesized.

2. Synthesis of Intermediate B

The intermediate N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-trimethylsilanamine was synthesized through the following reaction pathway.

In a flame-dried 5,000 ml Schlenk flask, 200 g (1.622 mol, 1 equivalent) of intermediate A, 180 g (1.784 mol, 1.1 equivalent) of triethylamine, and 194 g (1.784 mol, 1.1 equivalent) of chlorotrimethylsilane were mixed in 3,000 ml THF under a nitrogen atmosphere. Stirring over 12 hours gave a white suspension. After the reaction was completed, the suspension was filtered to obtain a filtrate, and the solvent and volatile side reactants were removed under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 152 g (yield: 48%) of N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-trimethylsilanamine, a transparent liquid compound. did

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ6.48~5.96, 2.79~2.69 (m, 4H, CpH), δ2.67~2.60 (m, 2H, - CH ₂ -), δ2.35~2.27 (m, 2H, -CH ₂ -), δ1.61~1.45 (m, 2H, -CH ₂ -), δ0.07(s, 9H, -Si(CH ₃ ) It was confirmed that the target compound was synthesized by confirming the characteristic peak of ₃ ).

3. Synthesis of Intermediate C

The intermediate N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-triethylsilanamine was synthesized through the following reaction pathway.

In a flame-dried 500 ml Schlenk flask, 20 g (0.16 mol, 1 equiv.) of intermediate A, 18.1 g (0.16 mol, 1 equiv.) of triethylamine, and 26.9 g (0.16 mol, 1 equiv.) of chlorotriethylsilane were mixed with nitrogen in 300 ml Tol. The mixture was stirred for 12 hours or more under an atmosphere to prepare a white suspension. After the reaction was completed, the suspension was filtered to obtain a filtrate, and the solvent and volatile side reactants were removed under reduced pressure. Subsequently, the remaining light yellow liquid was distilled under reduced pressure to obtain 19.15 g of N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-triethylsilanamine, a transparent liquid compound (yield: 49%). obtained.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ6.49~5.97, 2.80~2.69 (m, 4H, CpH), δ2.71~2.63 (m, 2H, - CH ₂ -), δ2.36~2.28 (m, 2H, -CH ₂ -), δ1.63~1.47 (m, 2H, -CH ₂ -), δ1.02~0.98 (t, 9H, -(CH ₃ ) ₃ ), δ0.57~0.51 (q, 6H, -Si-(CH ₂ ) ₃ -), δ0.1 (s, 1H, -NH-), confirming the characteristic peaks to confirm that the target compound was synthesized. Confirmed.

4. Synthesis of Intermediate D

The intermediate N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1-dimethylsilanamine was synthesized through the following reaction pathway.

In a flame-dried 1,000 ml Schlenk flask, 20 g (0.16 mol, 1 equiv.) of intermediate A, 18.1 g (0.16 mol, 1 equiv.) of triethylamine, and 16.9 g (0.16 mol, 1 equiv.) of chlorodimethylsilane were mixed with nitrogen in 500 ml Tol. The mixture was stirred for 12 hours or more under an atmosphere to prepare a yellow suspension. After the reaction was completed, the suspension was filtered to obtain a filtrate, and the solvent and volatile side reactants were removed under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 23 g (yield: 79%) of N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1-dimethylsilanamine, a transparent liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ° C), δ6.45-5.94, 2.78-2.67 (m, 4H, CpH), δ4.72-4.70 (m, 1H, - SiH), δ2.70~2.61 (m, 2H, -CH ₂ -), δ2.32~2.25 (m, 2H, -CH ₂ -), δ1.60~1.44 (m, 2H, -CH ₂ -) , δ 0.1 ~ 0.09 (s, 6H, -Si(CH ₃ ) ₂ ) by confirming the characteristic peak, it was confirmed that the target compound was synthesized.

5. Synthesis of Cyclopentadienpropyltrimethylsilane Hafnium(IV)

Cyclopentadienpropyltrimethylsilane Hafnium (IV) was synthesized through the following reaction pathway.

In a flame-dried 1,000 ml Schlenk flask, 108.6 g (0.55 mol, 1 equivalent) of intermediate B and 202 ml (0.55 mol, 1 equivalent) of Tetrakis (dimethylamino) hafnium (2.5 M) were mixed in 500 ml Hexane under a nitrogen atmosphere for 12 After stirring for an hour or longer, a pale yellow product was obtained. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 74 g (yield: 29%) of Cyclopentadienpropyltrimethylsilane Hafnium (IV), a pale yellow liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ° C), δ5.97-5.76, 3.08-3.05 (m, 4H, CpH), δ3.08-3.05 (m, 2H, - CH ₂ -), δ2.92 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ2.51~2.48 (m, 2H, -CH ₂ -), δ1.62~1.56 (m, 2H , -CH ₂ -), and δ0.21 (s, 9H, -Si(CH ₃ ) ₃ ) characteristic peaks were confirmed to confirm that the target compound was synthesized.

6. Synthesis of Cyclopentadienpropyltrimethylsilane Zirconium (IV)

Cyclopentadienpropyltrimethylsilane Zirconium (IV) was synthesized through the following reaction pathway.

In a flame-dried 250㎖ Schlenk flask, 12g (0.06mol, 1equivalent) of Intermediate B and 15g (0.06mol, 1equivalent) of Tetrakis(dimethylamino)zirconium were stirred in 100㎖ Hexane under a nitrogen atmosphere for more than 12 hours to obtain a pale yellow color. of the product was prepared. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 3 g (yield: 13%) of Cyclopentadienpropyltrimethylsilane Zirconium (IV), a pale yellow liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ6.00~5.78 (m, 4H, CpH), δ3.07~3.04 (m, 2H, -CH ₂ -) , δ2.88 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ2.52~2.49 (m, 2H, -CH ₂ -), δ1.63~1.57 (m, 2H, -CH ₂ -), δ 0.22 (s, 9H, -Si(CH ₃ ) ₃ ) by checking the characteristic peaks, it was confirmed that the target compound was synthesized.

7. Synthesis of Cyclopentadienpropyltriethylsilane Hafnium(IV)

Cyclopentadienpropyltriethylsilane Hafnium (IV) was synthesized through the following reaction pathway.

In a flame-dried 250㎖ Schlenk flask, 8g (0.03mol, 1equivalent) of Intermediate C and 12㎖ (0.03mol, 1equivalent) of Tetrakis(dimethylamino)hafnium (2.5M) were stirred in 100㎖ Hexane under a nitrogen atmosphere for 12 hours. A pale yellow product was obtained by further stirring. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 2 g (yield: 12%) of Cyclopentadienpropyltriethylsilane Hafnium (IV), a pale yellow liquid compound.

8. Synthesis of Cyclopentadienpropyltriethylsilane Zirconium (IV)

Cyclopentadienpropyltriethylsilane Zirconium (IV) was synthesized through the following reaction pathway.

In a flame-dried 250㎖ Schlenk flask, 8g (0.03mol, 1equivalent) of Intermediate C and 8.2g (0.03mol, 1equivalent) of Tetrakis(dimethylamino)zirconium were stirred in 100㎖ Hexane under a nitrogen atmosphere for more than 12 hours, and A yellow product was prepared. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 2.5 g (yield: 18%) of Cyclopentadienpropyltriethylsilane Zirconium (IV), a pale yellow liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ6.03~5.81 (m, 4H, CpH), δ3.06~2.89 (m, 2H, -CH ₂ -) , δ2.89 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ2.54~2.50(m, 2H, -CH ₂ -), δ1.63~1.57 (m, 2H, -CH _{2 -} ), δ1.12~1.08 (t, 9H, -(CH ₃ ) ₃ ), δ0.69~0.63 (q, 6H, -Si-(CH ₂ ) ₃ -) by confirming the characteristic peaks of the target compound It was confirmed that this was synthesized.

9. Synthesis of Cyclopentadienpropyltetramethylsilanamine Hafnium(IV)

Cyclopentadienpropyltetramethylsilanamine Hafnium (IV) was synthesized through the following reaction pathway.

In a flame-dried 250㎖ Schlenk flask, 3g (0.016mol, 1equivalent) of intermediate D and 5.34g (0.016mol, 1equivalent) of Tetrakis(dimethylamino) hafnium were stirred in 100㎖ Hexane under a nitrogen atmosphere for 12 hours or more to A yellow product was prepared. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 7g (yield: 87%) of Cyclopentadienpropyltetramethylsilanamine Hafnium (IV), a pale yellow liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ℃), δ5.99~5.78 (m, 4H, CpH), δ3.09~3.06 (m, 2H, -CH ₂ -) , δ2.91 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ 2.54 to 2.49 (m, 6H, -Si(N(CH ₃ ) ₂ ), δ 2.52 to 2.49 (m, 2H, -CH ₂ -), δ1.66~1.60 (m, 2H, -CH ₂ -), δ0.22 (s, 6H, -Si(CH ₃ ) ₂ ) by confirming the characteristic peaks, It was confirmed that it was synthesized.

10. Synthesis of Cyclopentadienpropyltetramethylsilanamine Zirconium(IV)

Cyclopentadienpropyltetramethylsilanamine Zirconium (IV) was synthesized through the following reaction pathway.

In a flame-dried 250㎖ Schlenk flask, 3g (0.016mol, 1equivalent) of intermediate D and 4.02g (0.016mol, 1equivalent) of Tetrakis(dimethylamino)zirconium were stirred in 100㎖ Hexane under a nitrogen atmosphere for more than 12 hours to A yellow product was prepared. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. Subsequently, the remaining pale yellow liquid was distilled under reduced pressure to obtain 5 g (yield: 75%) of Cyclopentadienpropyltetramethylsilanamine Zirconium (IV), a pale yellow liquid compound.

As a result of analyzing the product by ¹ H-NMR (400 MHz, C ₆ D ₆ , 25 ° C), δ 6.01 to 5.80 (m, 4H, CpH), δ 3.07 to 3.05 (m, 2H, -CH ₂ -), δ2.87 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ2.54 to 2.51 (m, 2H, -CH ₂ -), δ2.53 (s, 6H, -Si(N(CH ₃ ) ₂ ), δ1.66~1.61 (m, 2H, -CH ₂ -), δ0.23 (s, 6H, -Si(CH ₃ ) ₂ ) confirmed that the desired compound was synthesized by checking the characteristic peaks did

[Example 1]

To perform the HfSiO _x deposition process, a 6-inch p-type Si wafer is placed in the reaction chamber, the inside of the reaction chamber is purged with argon (Ar) gas, and atomic layer deposition equipment (CN1 Co., Ltd. 6" ATOMIC PREMIUM ) was used to deposit a dielectric film of HfSiO _x by injecting a precursor and an oxidizing gas, ozone (O ₃ ), in an atmosphere of 200 to 350 ° C. A deposition experiment was conducted using Cyclopentadienpropyltrimethylsilane Hafnium (IV) as the precursor.

At this time, in order to check the change rate of the deposited thin film thickness (GPC) according to the temperature, the process temperature was spilt in the reaction temperature range of 200 to 350 ° C., and the GPC change (Å / cycle) of the HfSiO _x thin film according to the process temperature was measured. The results of measuring the deposition rate are shown in Table 1 and FIG. 2 below.

reaction temperature range HfSiOx deposition rate (Å/cycle) 200 0.71 250 0.81 280 0.96 300 One 310 1.01 320 1.07 330 1.1 340 1.2 350 1.31

In addition, in order to confirm the incubation cycle of the process, the process cycle was split into 1 to 200 cycles to confirm the deposition rate according to the number of cycles, and the results are shown in FIG. 8.

In addition, in order to supply a stable precursor for forming a dielectric film, the precursor storage container (Canister) was heated to 140 ° C or higher, argon (Ar) gas was used as a carrier gas and supplied to the reactor, and an ozone generator was used as a reaction gas for oxidation. Ozone generated through the reactor was supplied to the reactor.

In addition, atomic layer deposition conditions are shown in Table 2 below, and a thin film was deposited by repeating the HfSiO _x dielectric film deposition process cycle using this process as one cycle.

Flow rate of argon gas to purge the inside of the reaction chamber 1000 sccm Precursor supply time for dielectric film formation 6s Precursor Ar purge time for dielectric film formation 15s Oxidizing gas supply time 13s Oxidizing gas (ozone (O ₃ )) supply concentration 180 GNM oxidizing gas purge 15s

As a result of analyzing the thin film formed by the above deposition conditions by XRD, it was confirmed that a HfSiOx dielectric film was formed as shown in FIG. 4 .

In addition, as a result of measuring the contents of Hf, O, Si, and carbon in the thin film through XPS analysis of the thin film produced by the ALD deposition process at 300 ° C, Hf 20.4at%, Si 14.7at%, O 58.9at% It was confirmed that the atomic ratio of Hf : Si : O was 1 : 0.72 : 2.89. Separately, the composition ratio of the sample using oxygen plasma as an oxidizing agent was 19.5 at% Hf, 19.3 at% Si, and 59.4 at% O, confirming that the atomic ratio of Hf: Si: O was 1: 0.99: 3.05. In any case, it was shown that HfSiO _x thin films were formed.

In addition, as a result of measuring the density of the thin film by XRR analysis, the density of the HfSiO _x thin film of _the present invention was analyzed. The density of was found to be 5.32 g/cm 3 .

From these results, it was confirmed that a high-quality thin film containing a Group 4 transition metal can be manufactured through a thin film formation process using the precursor according to the present invention.

Although the present invention has been described with preferred embodiments as described above, it is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of not departing from the spirit of the present invention. and change is possible. Such modifications and variations are to be regarded as falling within the scope of this invention and the appended claims.

Claims (10)

A precursor for forming a thin film containing a Group 4 transition metal, characterized in that it comprises an organometallic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,
M is Ti, Zr, or Hf;
X is a hydrogen atom, a C ₁ -C ₅ alkyl group, NR ₄ R ₅ or OR ₆ ;
R ₁ to R ₆ may be the same as or different from each other, and each independently represent a hydrogen atom or a C ₁ -C ₅ straight-chain, branched or cyclic alkyl group;
Any one of R ₁ may be an alkylamine group,
n is a natural number of 1, 2 or 3;
The method of claim 1,
A precursor for forming a thin film containing a Group 4 transition metal, characterized in that it further comprises a solvent.
The method of claim 2,
The solvent is a precursor for forming a thin film containing a Group 4 transition metal, characterized in that any one or more of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines.
The method of claim 2,
The solvent is a precursor for forming a thin film containing a group 4 transition metal, characterized in that contained in 1 to 99% by weight relative to the total weight of the precursor for forming a group 4 transition metal thin film.
A method of forming a thin film containing a Group 4 transition metal, comprising depositing a metal thin film on a substrate using the precursor for forming a Group 4 transition metal thin film according to claim 1 or 2.
The method of claim 5,
The group 4 transition metal thin film is a method of forming a thin film containing a group 4 transition metal, characterized in that deposited by atomic layer deposition or chemical vapor deposition.
The method of claim 5,
A method of forming a thin film containing a group 4 transition metal, characterized in that it comprises the step of vaporizing the precursor for forming a thin film containing a group 4 transition metal and transferring it into a chamber.
The method of claim 5,
In the deposition step,
positioning a substrate within the chamber;
supplying the Group 4 transition metal-containing precursor composition for forming a thin film into the chamber;
supplying a reactive gas or plasma of a reactive gas into the chamber;
processing in the chamber by any one or more means of heat treatment, plasma treatment, and light irradiation;
Group 4 transition metal-containing thin film forming method comprising a.
The method of claim 8,
The depositing step is a method of forming a thin film containing a Group 4 transition metal, characterized in that carried out at 250 to 400 ℃.
A semiconductor device comprising a Group 4 transition metal-containing thin film prepared by the method of forming a Group 4 transition metal-containing thin film of claim 5.

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