KR102679322B1 - 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 is characterized by comprising an organometallic compound represented by the following formula (1).
[Formula 1]

_{In Formula 1 ,} M _{is Ti} , Zr _, or Hf, , each independently 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.

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 thin film containing the Group 4 transition metal. {PRECURSOR FOR FILM DEPOSITION, DEPOSITION METHOD OF FILM AND SEMICONDUCTOR DEVICE OF THE SAME }

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. More specifically, it relates to atomic layer deposition (ALD). ) or a precursor that contains a Group 4 transition metal and silicon (Si) used in a chemical vapor deposition (CVD) process and can form thin films such as Group 4 transition metal-containing thin films, transition metal silicates, and silicon-doped metal-containing thin films, It relates to a method of forming a thin film containing a Group 4 transition metal using this method and a semiconductor device including the thin film containing the 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 characteristics 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.

One of these organometallic compounds is a precursor of an organometallic compound in the form of a complex compound containing a cyclopentadienyl group. In particular, an organometallic compound precursor that forms a cross-linked structure between the cyclopentadienyl group and the central metal atom can be used as a thin film. It is known to be effective in forming

For example, in Republic of Korea Patent Publication No. 10-1263454, a cross-linked 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 stepped coating. It has excellent properties and shows excellent properties as a precursor that does not decompose even when stored at high temperatures for a long time.

In addition, Republic of Korea Patent Publication No. 10-1959519 discloses a technology for forming a transition metal silicate thin film using an organometallic compound containing metal atoms and silicon atoms. By adopting a cross-linked structure with high thermal stability, a single precursor A transition metal silicate thin film can be formed.

In Korean Patent Publication No. 10-2019-0108281, the applicant used an organometallic compound that formed a cross-linked structure between a central metal and a cyclopentadienyl group to create a precursor that has excellent thermal stability and can solve problems occurring during the micronization process. It has been developed.

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

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

The present invention was developed in consideration of the above-described prior technologies, and its purpose is to provide a precursor for forming a Group 4 transition metal silicate (MSiO _x ) thin film that has excellent thermal stability and is suitable for high temperature deposition.

Additionally, the purpose is to provide a precursor for forming a Group 4 transition metal-containing thin film with increased stability through a cross-linked organometallic compound.

Additionally, the purpose is to provide a precursor capable of forming a transition metal silicate thin film by applying an organometallic compound containing a transition metal and silicon atoms as a precursor.

Another purpose 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 Group 4 transition metal containing metal thin film.

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 by comprising an organometallic compound represented by the following formula (1).

[Formula 1]

In Formula ₁ , _{M is} Ti, _{Zr ,} or Hf, Or it is a straight-chain, branched or cyclic alkyl group of C ₁ -C ₅ , any one of 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. there is.

Additionally, 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 Group 4 transition metal-containing thin film according to the present invention includes the step of depositing a Group 4 transition metal-containing thin film on a substrate using the precursor for forming the Group 4 transition metal-containing thin film.

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

Additionally, it may include vaporizing the precursor for forming a thin film containing a Group 4 transition metal and transferring it into the chamber.

In addition, the depositing step includes placing a substrate in a chamber, supplying a precursor composition for forming a thin film containing a Group 4 transition metal into the chamber, supplying a reactive gas or a plasma of a reactive gas into the chamber, It may include treatment in a chamber by any one or more of heat treatment, plasma treatment, and light irradiation, 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 of forming a group 4 transition metal-containing thin film.

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

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

In addition, by using the precursor, a method of forming a thin film containing a Group 4 transition metal and a method of manufacturing various semiconductor devices including the Group 4 transition metal containing thin film can be provided.

1 is a conceptual diagram showing the thin film formation process using the precursor of the present invention.
Figure 2 is a graph measuring GPC changes 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.
Figure 4 shows the XRD analysis results of the HfSiOx thin film formed through the 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 limited to their common 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 must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.

The precursor for forming a Group 4 transition metal-containing thin film according to the present invention is characterized by containing an organometallic compound represented by the following formula (1).

[Formula 1]

_{In Formula 1 ,} M _{is Ti} , Zr _, or Hf, , each independently 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.

The above organometallic compounds can be prepared through conventional ligand synthesis methods. That is, as shown in Schemes 1 to 3 below, it is prepared through the first step of reacting cyclopentane and an alkylamino compound, the second step of reacting the reaction product with an alkyl silicon compound, and the third step of reacting the reaction product with a zirconium compound. can do.

[Scheme 1]

[Scheme 2]

[Scheme 3]

The organometallic compound represented by Formula 1 specifically includes, but is not limited to, organometallic compounds selected from the structures below.

The precursor of the present invention may additionally include a solvent. The solvent may be any one of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, tertiary amines, or mixtures thereof. 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 containing or not containing a solvent can be vaporized, and the deposition process can be performed by supplying it into the chamber. It is desirable to appropriately select and use a soluble solvent according to the properties of the organometallic compound. That is, depending on the type of organometallic compound, if it exists in a liquid state at room temperature, the deposition process can be performed without a separate solvent.

The method of forming a Group 4 transition metal-containing thin film of the present invention is characterized by comprising the step of depositing a Group 4 transition metal-containing thin film on a substrate using the precursor for forming the Group 4 transition metal-containing thin film.

At this time, the precursor for forming the Group 4 transition metal-containing thin film 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 precursor for forming the Group 4 transition metal-containing thin film. there is.

The method for producing a Group 4 transition metal-containing thin film using a precursor containing an organometallic compound represented by Formula 1 is the method of producing a metal thin film by conventional deposition, except for using an organometallic compound represented by Formula 1 as a metal precursor. It can be carried out depending on the manufacturing method, and specifically, it can be carried out by methods such as chemical vapor deposition (CVD) or atomic layer deposition (ALD).

That is, supplying an organometallic compound represented by Formula 1 onto a substrate for forming a metal thin film existing in a reactor, supplying a reactive gas into the reactor, and performing a process selected from the group consisting of heat treatment, plasma treatment, and light irradiation. It may be prepared by a manufacturing method comprising carrying out a treatment process for the species.

Referring to FIG. 1, when explaining the thin film formation process, 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 ( 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 reactor (Figure 1(b)). Afterwards, when a reactive gas is supplied, metal atoms and silicon atoms are simultaneously deposited on the surface of the substrate, thereby forming a thin film of transition metal silicate (MSiO _x ).

The substrate for forming the Group 4 transition metal-containing thin film can be used without particular restrictions as long as it is used in semiconductor manufacturing and needs to be coated with a metal thin film due to technical functions. Specifically, silicon substrate (Si), silica substrate (SiO ₂ ), silicon nitride substrate (SiN), silicon oxynitride substrate (SiON), titanium nitride substrate (TiN), tantalum nitride substrate (TaN), and tungsten substrate. (W) or a noble metal substrate, such as 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 Formula 1 may be transferred through a volatilized gas, a direct liquid injection method, or a liquid transfer method in which the organometallic compound is dissolved in an organic solvent and then transferred may be used. The method of transferring the precursor as a volatilized gas is to place the container containing the precursor in a thermostat and evaporate the precursor by bubbling it with an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to form a metal thin film. It can be carried out by transferring it onto a substrate, or by using a liquid delivery system (LDS) to change the liquid precursor into a gas phase through a vaporizer and then transferring it onto the substrate for forming a metal thin film.

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

This solvent must have the property of dissolving solid substances or be capable of dissolving and dispersing liquid substances. In addition, considering the boiling point, density, and vapor pressure conditions of the solvent, the viscosity reduction effect and 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 supplying the organometallic compound represented by Formula 1 into the chamber, silicon (Si), titanium (Ti), and Select a metal precursor containing one or more metals (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, SiH(N(CH ₃ ) ₂ is used. ) 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 , etc. may be used.

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

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

In addition, before the supply of the reactive gas after the supply step of the metal precursor, it helps the metal precursor of Formula 1 and optionally the second metal precursor move onto the substrate, or ensures an appropriate pressure for deposition in the reactor, and also, the chamber In order to release impurities present within 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 within the reactor. At this time, it is preferable that the inert gas is spread so that the pressure within the reactor is 1 to 5 Torr.

After completing the supply of the above-described metal precursors, a reactive gas is supplied into the reactor, and one type of 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), and nitrous oxide. Any one or a mixture of nitrogen (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and silane (SiH ₄ ) may be used. When carried out in the presence of an oxidizing gas such as water vapor, oxygen, ozone, etc., a metal oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, silane, etc., a thin film of a single metal or metal nitride may be formed. You can.

In addition, the heat treatment, plasma treatment, or light irradiation treatment process is intended to provide heat 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 with a desired physical state and composition at a sufficient growth rate, the treatment process is preferably performed so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 300 to 500°C. .

In addition, during the treatment process, as described above, in order to help the movement of the reactive gas onto the substrate, to ensure 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 processing processes of adding the metal precursor, adding the reactive gas, and adding the inert gas are performed as one cycle. A metal-containing thin film can be formed by repeating the process one or more cycles.

Specifically, when an oxidizing gas is used as a reactive gas, the metal-containing thin film produced may include a metal oxide of the following formula (2).

[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, and M" is derived from the second metal precursor, silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta) and lanthanide atoms.

This method of manufacturing a thin film containing a Group 4 transition metal uses a metal precursor with excellent thermal stability, which allows the deposition process to be performed at a higher temperature than before, and eliminates particle contamination or impurities such as carbon due to thermal decomposition of the precursor. High purity metal, metal oxide or metal nitride thin films can be formed without contamination. Accordingly, the group 4 transition metal-containing thin film formed according to the manufacturing method of the present invention is useful for high dielectric material films in semiconductor devices, especially DRAM and CMOS in semiconductor memory devices.

In another embodiment, a group 4 transition metal-containing thin film formed by the method for forming a 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 (MIM) for random access memory (RAM).

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

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

1. Synthesis of Intermediate A

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

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

The product was analyzed by ¹ H-NMR (400MHz, C ₆ D ₆ , 25℃), δ6.46~5.90, 2.78~2.66 (m, 4H, CpH), δ2.51~2.43 (m, 2H, - CH ₂ -), δ2.31~2.23(m, 2H, -CH ₂ -), δ1.55~1.39 (m, 2H, -CH ₂ -), δ0.46(s, 2H, NH ₂ ) characteristics By checking 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 route.

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 dissolved in 3,000 ml THF under a nitrogen atmosphere. A white suspension was prepared by stirring for more than 12 hours. After the reaction was completed, the suspension was filtered to obtain a filtrate, and then the solvent and volatile side reactants were removed under reduced pressure. The remaining light yellow liquid was then distilled under reduced pressure to obtain 152g (yield: 48%) of N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-trimethylsilanamine, a transparent liquid compound. did.

The product was analyzed by ¹ H-NMR (400MHz, 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 checking 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 route.

In a flame-dried 500 ml Schlenk flask, 20 g (0.16 mol, 1 equivalent) of Intermediate A, 18.1 g (0.16 mol, 1 equivalent) of Triethylamine, and 26.9 g (0.16 mol, 1 equivalent) of chlorotriethylsilane were dissolved in nitrogen in 300 ml Tol. A white suspension was prepared by stirring under an atmosphere for more than 12 hours. After the reaction was completed, the suspension was filtered to obtain a filtrate, and then the solvent and volatile side reactants were removed under reduced pressure. The remaining light yellow liquid was then distilled under reduced pressure to produce 19.15 g (yield: 49%) of N-(3-(cyclopenta-2,4-dien-1-yl)propyl)-1,1,1-triethylsilanamine, a transparent liquid compound. Obtained.

The product was analyzed by ¹ H-NMR (400MHz, 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-) were confirmed 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 route.

In a flame-dried 1,000 ml Schlenk flask, 20 g (0.16 mol, 1 equivalent) of Intermediate A, 18.1 g (0.16 mol, 1 equivalent) of Triethylamine, and 16.9 g (0.16 mol, 1 equivalent) of chlorodimethylsilane were dissolved in nitrogen in 500 ml Tol. A yellow suspension was prepared by stirring under an atmosphere for more than 12 hours. After the reaction was completed, the suspension was filtered to obtain a filtrate, and then the solvent and volatile side reactants were removed under reduced pressure. The remaining light yellow liquid was then 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.

The product was analyzed by ^1H -NMR (400MHz, C ₆ D ₆ , 25℃), 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 -) , δ0.1~0.09 (s, 6H, -Si(CH ₃ ) ₂ ) was confirmed to confirm that the target compound was synthesized.

5. Synthesis of Cyclopentadienpropyltrimethylsilane Hafnium(Ⅳ)

Cyclopentadienpropyltrimethylsilane Hafnium(IV) was synthesized using the following reaction route.

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 reacted in 500 mL of hexane under a nitrogen atmosphere for 12 days. After stirring for more than an hour, a light yellow product was prepared. After the reaction was completed, the solvent and volatile side reactants were removed from the product under reduced pressure. The remaining light yellow liquid was then distilled under reduced pressure to obtain 74 g (yield: 29%) of Cyclopentadienpropyltrimethylsilane Hafnium (IV), a light yellow liquid compound.

The product was analyzed by ¹ H-NMR (400MHz, C ₆ D ₆ , 25℃), 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 ) were confirmed to confirm that the target compound was synthesized.

6. Synthesis of Cyclopentadienpropyltrimethylsilane Zirconium(Ⅳ)

Cyclopentadienpropyltrimethylsilane Zirconium(IV) was synthesized using the following reaction route.

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

The product was analyzed by ^1H -NMR (400MHz, 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 -), δ0.22 (s, 9H, -Si(CH ₃ ) ₃ ) was confirmed to confirm that the target compound was synthesized.

7. Synthesis of Cyclopentadienpropyltriethylsilane Hafnium(Ⅳ)

Cyclopentadienpropyltriethylsilane Hafnium(IV) was synthesized using the following reaction route.

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

8. Synthesis of Cyclopentadienpropyltriethylsilane Zirconium(Ⅳ)

Cyclopentadienpropyltriethylsilane Zirconium(IV) was synthesized using the following reaction route.

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

The product was analyzed by ¹ H-NMR (400MHz, 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 -) and identify the target compound. It was confirmed that this was synthesized.

9. Synthesis of Cyclopentadienpropyltetramethylsilanamine Hafnium(Ⅳ)

Cyclopentadienpropyltetramethylsilanamine Hafnium(IV) was synthesized using the following reaction route.

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

The product was analyzed by ^1H -NMR (400MHz, 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 ), δ2.54~2.49 (m, 6H, -Si(N(CH ₃ ) ₂ ), δ2.52~2.49 (m, The target compound was confirmed by checking the characteristic peaks of 2H, -CH ₂ -), δ1.66~1.60 (m, 2H, -CH ₂ -), δ0.22 (s, 6H, -Si(CH ₃ ) ₂ ). It was confirmed that it was synthesized.

10. Synthesis of Cyclopentadienpropyltetramethylsilanamine Zirconium(Ⅳ)

Cyclopentadienpropyltetramethylsilanamine Zirconium(IV) was synthesized using the following reaction route.

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

The product was analyzed by ¹ H-NMR (400MHz, C ₆ D ₆ , 25°C), δ6.01~5.80 (m, 4H, CpH), δ 3.07~3.05 (m, 2H, -CH ₂ -), δ2.87 (s, 12H, -(N(CH ₃ ) ₂ ) ₂ ), δ2.54~2.51 (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 ) characteristic peaks were confirmed to confirm that the target compound was synthesized. did.

[Example 1]

To perform the _HfSiO ) _was used to deposit a dielectric film _of HfSiO

At this time, in order to check the rate of change in the thickness of the deposited thin film (GPC) according to the temperature, the process temperature was Spilted in the reaction temperature range of 200 to 350 ℃ 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 Figure 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 check the incubation cycle of the process, the process cycle was split into 1 to 200 cycles to check 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 over 140℃, and 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. The ozone generated through the reactor was supplied to the reactor.

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

Argon gas flow rate 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 180GNM Oxidizing gas purge 15s

As a result of analyzing the thin film formed under the above deposition conditions by XRD, it was confirmed that an 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 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 the 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 all cases, it was found that a HfSiO _x thin film was formed.

In addition, as a result of measuring the density of the thin film through XRR analysis, the density of _{the HfSiO} The density was confirmed to be 5.32g/cm3.

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

The present invention has been described with reference to preferred embodiments as described above, but is not limited to the above embodiments and may be modified in various ways by those skilled in the art without departing from the spirit of the invention. and can be changed. Such modifications and variations should be considered to fall within the scope of the present invention and the appended claims.

Claims (10)

A precursor for forming a Group 4 transition metal-containing thin film, characterized in that it contains an organometallic compound represented by the following formula (1).

[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 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,
Any one of R ₁ may be an alkylamine group,
n is a natural number of 1, 2 or 3.
In claim 1,
A precursor for forming a thin film containing a Group 4 transition metal, characterized in that it additionally contains a solvent.
In claim 2,
A precursor for forming a Group 4 transition metal-containing thin film, wherein the solvent is one or more of C ₁ -C ₁₆ saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, and tertiary amines.
In claim 2,
A precursor for forming a Group 4 transition metal-containing thin film, wherein the solvent is contained 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.
A method of forming a Group 4 transition metal-containing thin film, comprising the step of 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.
In claim 5,
A method of forming a thin film containing a Group 4 transition metal, wherein the Group 4 transition metal thin film is deposited by atomic layer deposition or chemical vapor deposition.
In claim 5,
A method of forming a thin film containing a Group 4 transition metal, comprising the step of vaporizing the precursor for forming a Group 4 transition metal-containing thin film and transferring it into a chamber.
In claim 5,
The deposition step is,
Positioning a substrate within the chamber;
Supplying a precursor composition for forming a thin film containing a Group 4 transition metal into the chamber;
supplying a reactive gas or a plasma of a reactive gas into the chamber;
Processing within the chamber by any one or more of heat treatment, plasma treatment, and light irradiation;
A method of forming a thin film containing a Group 4 transition metal, comprising:
In claim 8,
A method of forming a thin film containing a Group 4 transition metal, characterized in that the deposition step is performed at 250 to 400 ° C.
A semiconductor device comprising a Group 4 transition metal-containing thin film manufactured by the Group 4 transition metal-containing thin film forming method of claim 5.