Auxiliary precursors, thin film precursor compositions, thin film forming methods, and semiconductor substrates manufactured by the methods

Abstract

The present invention relates to a kind of auxiliary precursor, thin film precursor composition, the thin film forming method using it and the semiconductor substrate manufactured by the method, provide the thin film precursor composition containing the compound of the predetermined structure showing the reaction stability to thin film precursor compound as auxiliary precursor, utilize the thin film precursor composition in the thin film deposition process to inhibit side reaction, and appropriately control thin film growth rate, and remove the process by-product in thin film, so as to even in the deposition of thin film on the substrate of complex structure, can greatly improve the step coverage, the thickness uniformity of thin film and resistivity characteristics, reduce corrosion and deterioration, improve the crystallinity of thin film, so as to improve the electrical characteristics of thin film.

Description

Technical Field

[0001] This invention relates to an auxiliary precursor, a thin film precursor composition comprising the same, a thin film formation method using the same, and a semiconductor substrate manufactured by the method. Specifically, it relates to suppressing side reactions to reduce the impurity concentration in the thin film and preventing corrosion and degradation of the thin film to improve the electrical properties of the thin film, and appropriately controlling the growth rate of the thin film so as to improve step coverage, thickness uniformity, and resistivity even when forming the thin film on a substrate with a complex structure, and an auxiliary precursor that does not decompose even when mixed with a thin film precursor, a thin film precursor composition comprising the same, a thin film formation method using the same, and a semiconductor substrate manufactured by the method. Background Technology

[0002] The integration density of memory and non-memory semiconductor devices is increasing daily, and as their structures become more complex, the importance of film quality and step coverage is gradually increasing when depositing various thin films onto substrates.

[0003] The semiconductor thin film is formed from metal nitride, silicon nitride, metal oxide, metal silicide, etc. The metal nitride thin film includes titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), AlN, TiSiN, TiAlN, TiBN, TiON, TiCN, etc., and is typically used as a silicon layer for impurity semiconductors and as a diffusion barrier for aluminum (Al), copper (Cu), etc., used as interlayer wiring materials. Tungsten (W) and molybdenum (Mo) metal thin films are used as adhesion layers during substrate deposition.

[0004] To ensure that the thin film deposited on the substrate possesses excellent and uniform physical properties, the formed film must exhibit high step coverage. Therefore, compared to chemical vapor deposition (CVD), which primarily utilizes gas-phase reactions, atomic layer deposition (ALD), which utilizes surface reactions, is increasingly employed. However, achieving 100% step coverage remains a challenge.

[0005] Furthermore, as a method to improve step coverage, a method to reduce the growth rate of the film has been proposed. However, when the deposition temperature is lowered in order to reduce the growth rate of the film, the residual amount of impurities such as carbon and chlorine in the film increases, thus significantly reducing the film quality.

[0006] Furthermore, when titanium tetrachloride (TiCl4) is used to deposit titanium nitride (TiN), a representative of the nitride metals, the resulting film may contain residual process byproducts such as chlorides, which can induce corrosion of metals such as aluminum and lead to film degradation due to the formation of non-volatile byproducts.

[0007] Therefore, there is a need to develop a method for forming thin films with complex structures, low residual impurities, and no corrosion of interlayer wiring materials, as well as a semiconductor substrate manufactured by this method. Furthermore, there is a need to develop auxiliary precursors that can provide uniform thickness and step coverage even with high aspect ratios due to the increase in the number of VNAND stacks to 128, 256, 512, etc., and that are difficult to decompose even when mixed with thin film precursors, thus providing excellent performance.

[0008] Prior art literature

[0009] Patent document: Korean Patent Publication No. 2006-0037241 Summary of the Invention

[0010] Technical issues

[0011] To address the aforementioned technical problems, the present invention aims to provide an auxiliary precursor, a thin film formation method thereon, and a semiconductor substrate manufactured by the method, which provides a low bandgap to significantly improve the quality of the thin film containing it, suppresses side reactions to appropriately regulate the thin film growth rate, and prevents corrosion and degradation by removing process byproducts from the thin film. Even when forming a thin film on a substrate with a complex structure, it can significantly improve step coverage, thin film thickness uniformity, and resistivity characteristics, and it will not decompose even when used in combination with a thin film precursor.

[0012] In addition, the purpose of this invention is to improve the crystallinity of the thin film, thereby improving the electrical properties of the thin film such as density and resistivity.

[0013] The above-described objectives and several other objectives of the present invention can all be achieved by means of the present invention described below.

[0014] Technical solution

[0015] To achieve the above objectives, the present invention provides an auxiliary precursor, which is a linear, branched, cyclic, or aromatic compound represented by Chemical Formula 1, and is used in combination with a film precursor compound.

[0016] Chemical Formula 1:

[0017] A n B m Xo Y i Z j

[0018] In the chemical formula 1, A is carbon or silicon, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3.

[0019] The auxiliary precursor may be the same as the auxiliary precursor. 1 Compared to the H-NMR spectrum, the spectrum obtained after mixing the auxiliary precursor and the film precursor compound at a 1:1 molar ratio and applying pressure was... 1 Compounds whose integral value at the top of the newly formed peak in the H-NMR spectrum is less than 0.1%.

[0020] In addition, the present invention provides a thin film precursor composition comprising an auxiliary precursor represented by chemical formula 1 as a linear, branched, cyclic, or aromatic compound, and a thin film precursor compound represented by chemical formula 2.

[0021] Chemical Formula 1:

[0022] A n B m X o Y i Z j

[0023] In the chemical formula 1, A is carbon or silicon; B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine, and are different from each other; n is an integer from 1 to 15; o is an integer greater than or equal to 1; m is from 0 to 2n+1; and i and j are integers from 0 to 3.

[0024] Chemical formula 2:

[0025] M x L y

[0026] In the chemical formula 2, x is an integer from 1 to 3, and M can be selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, T Among b, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, y is an integer from 0 to 6, and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand composed of two or more combinations selected from H, C, N, O, F, P, S, Cl, and Br.

[0027] The weight ratio of the auxiliary precursor to the film precursor compound can be 1:99 to 99:1.

[0028] The auxiliary precursor may be one or more compounds selected from those represented by chemical formulas 3 to 14.

[0029] Chemical formulas 3 to 14:

[0030]

[0031] In the chemical formulas 3 to 14, the lines represent bonds, and the points where the bonds connect without other elements are carbon atoms. The number of hydrogen atoms that satisfy the valence of carbon atoms is omitted.

[0032] The thin film precursor composition can be used in atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma-enhanced chemical vapor deposition (PECVD) processes.

[0033] In addition, the present invention provides a thin film forming method, which includes the following steps: injecting the above-mentioned thin film precursor composition into a chamber and adsorbing it onto the surface of a loaded substrate.

[0034] This invention may include the following steps:

[0035] Step i) involves vaporizing the thin film precursor composition and adsorbing it onto the surface of the substrate loaded in the chamber;

[0036] Step ii) involves first purging the interior of the chamber using purge gas;

[0037] Step iii), supplying the reaction gas into the chamber; and

[0038] Step iv) involves a second purging of the chamber using purging gas.

[0039] The thin film precursor composition can be transferred into an ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber via VFC, DLI, or LDS.

[0040] The ratio of the auxiliary precursor to the intracavitary loading (mg / cycle) of the film precursor composition can be 1:0.1 to 1:20.

[0041] The reactant gas can be a reducing agent, a nitrifying agent, or an oxidizing agent.

[0042] The deposition temperature of the thin film formation method can be 200–700°C.

[0043] The thin film can be an oxide film, a nitride film, or a metal film.

[0044] The film may include a multilayer structure with two or three layers.

[0045] In addition, the present invention provides a semiconductor substrate which is manufactured by the above-described thin film formation method.

[0046] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal capacitors, DRAM trench capacitors, 3D gate-all-around (GAA) capacitors, or 3D NAND.

[0047] Beneficial effects

[0048] According to the present invention, an auxiliary precursor is provided that adjusts the deposition rate to appropriately regulate the film growth rate, thereby improving step coverage and film quality even when forming films on substrates with complex structures.

[0049] In addition, an auxiliary precursor for thin film formation is provided, and a thin film formation method using the precursor and a semiconductor substrate manufactured by the method are further provided, wherein the auxiliary precursor for thin film formation exhibits reaction stability with the thin film precursor compound, so that during thin film formation, the adsorption of the thin film precursor compound is not hindered and process byproducts are reduced, thereby preventing corrosion and deterioration and improving the crystallinity of the thin film, thereby improving the resistivity and electrical properties of the thin film. Attached Figure Description

[0050] Figure 1 This is a graph showing the experimental results confirming whether the auxiliary precursor of the present invention decomposes when mixed with the film precursor compound, wherein the auxiliary precursor used in Example 1 is shown individually. 1 The H-NMR spectrum is shown in the upper image, representing the mixture of the auxiliary precursor and the film precursor compound. 1 The H-NMR spectrum is shown in the lower side panel. Detailed Implementation

[0051] The following provides a detailed description of the auxiliary precursor, the thin film precursor composition, the thin film formation method using the same, and the semiconductor substrate manufactured by the method.

[0052] The inventors of this invention have confirmed that when a thin film precursor compound is adsorbed onto the surface of a substrate loaded inside a cavity, if an auxiliary precursor having a specific structure that is not decomposed by the thin film precursor compound is also adsorbed, the adsorption of the thin film precursor compound is not hindered and process byproducts are reduced. This prevents corrosion and degradation and improves the crystallinity of the thin film, thereby significantly improving the resistivity and electrical properties of the thin film. Furthermore, it has been confirmed that when a composition comprising a thin film precursor compound and a specific auxiliary precursor is adsorbed onto the surface of a substrate loaded inside a cavity, the resistivity properties are unexpectedly significantly improved compared to adsorbing the thin film precursor compound first and then the auxiliary precursor onto the surface of the substrate loaded inside the cavity, or vice versa. Based on this, further research was conducted, and this invention was completed.

[0053] As a preferred embodiment, the thin film formation method may include the following steps: step i), vaporizing and adsorbing a thin film precursor composition containing the auxiliary precursor and the thin film precursor compound onto the surface of a substrate loaded in a chamber; step ii), performing a first purging of the chamber using a purge gas; step iii), supplying a reactive gas into the chamber; and step iv), performing a second purging of the chamber using a purge gas. In this process, the thin film growth rate is controlled, and even if the deposition temperature increases during thin film formation, the generated process byproducts are effectively removed. Therefore, this method has the advantages of improving the resistivity of the thin film and significantly improving step coverage.

[0054] In another preferred embodiment, the thin film formation method may include the following steps: step i), vaporizing the auxiliary precursor and the thin film precursor compound and adsorbing them onto the surface of the substrate loaded in the chamber; step ii), performing a first purging of the chamber using a purge gas; step iii), supplying a reaction gas into the chamber; and step iv), performing a second purging of the chamber using a purge gas. At this point, the thin film growth rate is controlled, and even if the deposition temperature increases during thin film formation, the generated process byproducts are effectively removed. Therefore, it has the advantages of improving the resistivity of the thin film and significantly improving step coverage.

[0055] The film precursor composition comprising the auxiliary precursor and the film precursor compound is preferably transferred into the chamber independently via VFC (gas flow control), DLI (direct liquid injection), or LDS (liquid transfer system), more preferably via LDS.

[0056] The thin film precursor composition comprising the auxiliary precursor and the thin film precursor compound is preferably used in atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma enhanced chemical vapor deposition (PECVD) processes, more preferably in atomic layer deposition (ALD) or plasma enhanced chemical vapor deposition (PECVD) processes.

[0057] The thin film precursor compound can be a thin film precursor compound represented by chemical formula 2, in which case the expected effects of the present invention are well achieved and the resistivity of the thin film is improved.

[0058] Chemical formula 2:

[0059] M x L y

[0060] In the chemical formula 2, x is an integer from 1 to 3, and M can be selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, T Among b, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, y is an integer from 0 to 6, and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand composed of two or more combinations selected from H, C, N, O, F, P, S, Cl, and Br.

[0061] In addition, the thin film precursor composition of the present invention includes an auxiliary precursor represented by chemical formula 1 as a linear, branched, cyclic or aromatic compound and a thin film precursor compound represented by chemical formula 2. In this case, the desired effect is well achieved and it has the advantage of improving the resistivity of the thin film.

[0062] Chemical Formula 1:

[0063] A n B m X o Y i Z j

[0064] In the chemical formula 1, A is carbon or silicon, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3.

[0065] Chemical formula 2:

[0066] M x L y

[0067] In the chemical formula 2, x is an integer from 1 to 3, and M can be selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, T Among b, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, y is an integer from 0 to 6, and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand composed of two or more combinations selected from H, C, N, O, F, P, S, Cl, and Br.

[0068] The auxiliary precursor and the film precursor compound may have a weight ratio of 1:99 to 99:1, 1:90 to 90:1, 1:85 to 85:1, or 1:80 to 80:1.

[0069] As an example, the auxiliary precursor can be a linear, branched, or cyclic compound represented by the chemical formula 1, wherein A is carbon or silicon, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are 0. In this case, the intended effects of the present invention are well achieved, and it has the advantage of improving the resistivity of the thin film.

[0070] X can be a halogen element, preferably fluorine, chlorine, bromine, or iodine, more preferably chlorine or bromine. Within this range, it has the advantages of reduced process byproducts and better adsorption on the substrate. Alternatively, as an example, X can be chlorine, which has the advantages of improving film crystallinity and effectively reducing process byproducts by suppressing side reactions.

[0071] As another preferred example, in chemical formula 1, X can be iodine or bromine, which has the advantage of being more suitable for processes requiring low-temperature deposition.

[0072] In a preferred embodiment, the auxiliary precursor may be a linear, branched, or cyclic compound represented by the chemical formula 1, wherein A is carbon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than 1, m is from 0 to 2n+1, and i and j are 0. In this case, the intended effects of the present invention are well achieved and the improved resistivity is exhibited.

[0073] In a preferred embodiment, the auxiliary precursor can be a linear, branched, or cyclic compound represented by the chemical formula 1, wherein A is carbon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than 1, m is from 0 to 2n+1, and i and j are 0. In this case, the expected effects of the present invention are well achieved and the improved resistivity, improved film crystallinity, and reduced process by-products due to suppression of side reactions are more effectively achieved.

[0074] In another preferred embodiment, the auxiliary precursor may comprise a hydrocarbon with an electron acceptor end group. The hydrocarbon may be a substance that is not reactive with the thin film precursor compound. When using the auxiliary precursor, the adsorption of the thin film precursor compound is not hindered, process byproducts are reduced, and the deposition rate is adjusted to appropriately reduce the thin film growth rate. Thus, even when forming a thin film on a substrate with a complex structure, step coverage and film quality can be improved, corrosion and degradation can be prevented, and the crystallinity of the thin film can be improved, thereby improving the resistivity and electrical properties of the thin film.

[0075] The hydrocarbon is preferably a compound having a structure in which one or more electron acceptor end groups selected from alkanes and cycloalkanes are substituted. In this case, it has the advantages of low reactivity and solubility, easy water management, and improved step coverage on trench structures with high aspect ratio when forming a thin film.

[0076] As a more preferred example, the hydrocarbon may include C1-C10 alkane or C3-C10 cycloalkane, preferably C3-C10 cycloalkane, which has the advantages of low reactivity and solubility and easy moisture management.

[0077] In this application, C1, C3, etc., represent the number of carbon atoms.

[0078] The cycloalkanes are preferably C3 to C10 monocycloalkanes. Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, so it is suitable for vapor deposition processes, but is not limited thereto.

[0079] Unless otherwise specified, the term "electron acceptor end group" as used in this invention refers to a functional group that can improve membrane quality when combined with a thin film precursor compound.

[0080] As an example, the electron acceptor terminal group can be an ortho-oriented or para-oriented passivation group.

[0081] Unless otherwise specified, the term "ortho- and para-oriented desensitizing groups" refers to desensitizing groups that exhibit ortho- and para-oriented orientation when using precursor compounds having a benzene ring.

[0082] As another example, the electron acceptor terminal group can be an electron acceptor with an electronegativity of 2.0 to 4.0, preferably an electron acceptor with an electronegativity of 2.0 to 3.0.

[0083] Unless otherwise specified, when using precursor compounds that do not have a benzene ring, functional groups that satisfy the electronegativity range may be used.

[0084] As a specific example, the electron acceptor terminal group can be a halogen element, preferably fluorine, chlorine, bromine, or iodine, more preferably bromine or iodine, which has the advantages of reducing process by-products and improving step coverage. Alternatively, as another example, X can be iodine, which is more suitable for processes requiring low-temperature deposition. In particular, X can be an iodine-based substance, which does not excessively increase the impurity content, thus being more effective in improving the film quality.

[0085] Regarding the reactivity of the hydrocarbon with the film precursor compound, an NMR peak is generated by comparing the H-NMR spectrum measured before mixing the hydrocarbon and the film precursor compound with the H-NMR spectrum measured after pressurizing the mixture at a molar ratio of 1:1 for 1 hour. When the integral value of the area of ​​this NMR peak is taken as the impurity content, the impurity content (%) is shown to be less than 0.1%. Therefore, when using an auxiliary precursor, the adsorption of the film precursor compound is not hindered, process byproducts can be reduced, and the deposition rate can be adjusted to appropriately reduce the film growth rate. Thus, even when forming a film on a substrate with a complex structure, step coverage and film quality can be improved, corrosion and deterioration can be prevented, the crystallinity of the film can be improved, thereby improving the resistivity and electrical properties of the film.

[0086] Based on the above-mentioned reactivity, the auxiliary precursor has the advantage of being easy to adjust the viscosity and vapor pressure of the film precursor compound without hindering the behavior of the film precursor compound.

[0087] As an example, the hydrocarbon exhibiting the above-mentioned reactivity and containing the electron acceptor end group can be a straight-chain or branched alkane compound or a cycloalkane compound substituted with halogen.

[0088] As a specific example, the material is selected from one or more of 1-iodobutane, 2-iodobutane, 2-iodo-3-methylbutane, 3-iodo-2,4-dimethylpentane, iodocyclohexane, iodocyclopentane, 1-bromobutane, 2-bromobutane, 2-bromo-3-methylbutane, 3-bromo-2,4-dimethylpentane, bromocyclohexane, and bromocyclopentane, preferably one or more of 1-iodobutane and 2-iodobutane. In this case, it has the advantages of not hindering the adsorption of the film precursor compound, effectively protecting the surface of the substrate as an auxiliary precursor, and effectively removing process by-products.

[0089] As described above, the hydrocarbon can be a halohydrocarbon, and as a specific example, it can be a compound represented by chemical formulas 3 to 14. The compounds represented by chemical formulas 3 to 14 can be selected independently, or mixtures thereof can be used.

[0090] Chemical formulas 3 to 14:

[0091]

[0092] In the chemical formulas 3 to 14, the lines represent bonds, and the points where the bonds connect without other elements are carbon atoms. The number of hydrogen atoms that satisfy the valence of carbon atoms is omitted.

[0093] The auxiliary precursor is preferably used in atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma enhanced chemical vapor deposition (PECVD) processes. In these processes, it has the advantages of not hindering the adsorption of the thin film precursor compound and effectively protecting the substrate surface as an auxiliary precursor while effectively removing process byproducts.

[0094] Preferably, the auxiliary precursor can be a liquid at room temperature (22°C) with a density of 0.8–2.5 g / cm³. 3 Or 0.8~1.7g / cm 3 The vapor pressure (20℃) can be 0.1~300mmHg or 1~300mmHg, and the solubility in water (25℃) can be below 200mg / L. Within this range, it has excellent effects on step coverage, film thickness uniformity and film quality improvement.

[0095] More preferably, the density of the auxiliary precursor may be 0.75–2.0 g / cm³. 3 Or 0.8~1.7g / cm 3 The vapor pressure (20℃) can be 1~260mmHg, and the solubility in water (25℃) can be below 160mg / L. Within this range, it has excellent effects on step coverage, film thickness uniformity and film quality improvement.

[0096] In another preferred embodiment, the thin film formation method of the present invention includes the step of injecting the thin film precursor composition into an ALD chamber and adsorbing it onto the surface of the loaded substrate. In this case, the thin film growth rate is appropriately increased, and the process byproducts generated during thin film formation are effectively removed, thus having the advantages of reducing impurities in the thin film and significantly improving crystallinity.

[0097] The thin film formation method may use a reducing agent, a nitriding agent, or an oxidizing agent as the reaction gas.

[0098] As an example, the deposition temperature of the thin film formation method is 200-700°C, preferably 250-500°C. Specific examples include 250-450°C, 250-320°C, 380-420°C, or 400-450°C. Within this range, it has the advantages of significantly improving thin film resistivity and step coverage.

[0099] In addition, the thin film precursor composition of the present invention can be an auxiliary precursor of a linear, branched, cyclic or aromatic compound represented by chemical formula 1; and a thin film precursor compound represented by chemical formula 2. In this case, the expected effects of the present invention are well realized and the high resistivity characteristics are exhibited.

[0100] Chemical Formula 1:

[0101] A n B m X o Y i Z j

[0102] Wherein, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is one or more of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently selected from one or more of oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer from 1 to 15, o is an integer greater than or equal to 1, m is from 0 to 2n+1, and i and j are integers from 0 to 3.

[0103] Chemical formula 2:

[0104] Mx L y

[0105] Wherein, x is an integer from 1 to 3, and M can be selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy Among Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, y is an integer from 1 to 6, and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand composed of two or more combinations selected from H, C, N, O, F, P, S, Cl, and Br.

[0106] In chemical formula 2, M is titanium, tungsten, molybdenum, silicon, hafnium, zirconium, indium, or germanium, preferably titanium, tungsten, molybdenum, or silicon.

[0107] In chemical formula 2, L can be a halogen element, preferably fluorine, chlorine, bromine, or iodine, more preferably chlorine or bromine. Within this range, there are advantages such as reduced process byproducts and better adsorption on the substrate. Alternatively, as an example, L can be chlorine, in which case there are advantages such as improved film crystallinity and even better reduction of process byproducts due to suppression of side reactions.

[0108] Compounds represented by Formula 2 are halogen-substituted tertiary alkyl compounds. Specific examples include titanium tetrachloride, 2-chloro-3-methyltitanium, 2-chloro-2-methyltitanium, titanium tetrabromide, 3-bromo-3-methyltitanium, 3-bromo-3-methyltitanium, titanium tetrachloride, 2-chloro-3-methyltungsten, 2-chloro-2-methyltungsten, tungsten tetrabromide, 3-bromo-3-methyltungsten, 3-bromo-3-methyltungsten, molybdenum tetrachloride, 2-chloro-3-methylmolybdenum, 2-chloro-2-methylmolybdenum, molybdenum tetrabromide, 3-bromo-3-methylmolybdenum, 3-bromo-3-methylmolybdenum, molybdenum tetrachloride, molybdenum tetrabrom ... The presence of one or more of the following substances results in significant removal of process byproducts, improved step coverage, and excellent adsorption on the substrate.

[0109] Unless otherwise specified, the term "conductive compound" as used in this invention refers to a substance that is conductive due to having electron donors or acceptors and that is affected by its structure and charge-movement oxidation state.

[0110] The specific examples described are those of compounds or conductive compounds represented by chemical formula 2, but are not limited to these, as long as they are thin film precursor compounds conventionally used in atomic layer deposition (ALD) methods.

[0111] As a specific example, it may include one or more selected from metal film precursor compounds, metal oxide film precursor compounds, metal nitride film precursor compounds, and silicon nitride film precursor compounds, wherein the metal is preferably selected from one or more selected from tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanides, actinides, gallium, tantalum, zirconium, ruthenium, copper, titanium, nickel, iridium, molybdenum, platinum, ruthenium, and iridium.

[0112] As an example, the metal film precursor, metal oxide film precursor, and metal nitride film precursor may be selected from one or more of metal halides, metal alkoxides, alkyl metal compounds, metal amino compounds, metal carbonyl compounds, and substituted or unsubstituted cyclopentadienyl metal compounds, but are not limited thereto.

[0113] As an example, the metal oxide film precursor may be independently selected from PtO, PtO2, RuO2, IrO2, SrRuO3, BaRuO3, and CaRuO3.

[0114] As a specific example, the metal film precursor, metal oxide film precursor, and metal nitride film precursor can be selected from titanium tetrachloride, germanium tetrachloride, tin tetrachloride, tris(isopropyl)ethylmethylaminogermanium, tetraethoxygermanium, tetramethyltin, and tetraethyltin, respectively. The following are some of the following: tin, bisacetylacetonatetin, trimethylaluminum, tetrakis(dimethylamino)germanium, bis(n-butylamino)germanium, tetrakis(ethylmethylamino)tin, tetrakis(dimethylamino)tin, Co2(CO)8(dicobaltoctacarbonyl), Cp2Co(biscyclopentadienylcobalt), Co(CO)3(NO)(cobalt tricarbonyl nitrosyl), and CpCo(CO)2(cabaltdicarbonyl cyclopentadienyl).

[0115] As an example, the silicon nitride film precursor may be selected from SiH4, SiCl4, SiF4, SiCl2H2, Si2Cl6, TEOS, DIPAS, BTBAS, (NH2)Si(NHMe)3, (NH2)Si(NHEt)3, (NH2)Si(NH n Pr)3、(NH2)Si(NH i Pr)3、(NH2)Si(NH n Bu)3、(NH2)Si(NH i Bu)3、(NH2)Si(NH t Bu)3, (NMe2)Si(NHMe)3, (NMe2)Si(NHEt)3, (NMe2)Si(NH n Pr)3、(NMe2)Si(NH iPr)3、(NMe2)Si(NH n Bu)3、(NMe2)Si(NH i Bu)3、(NMe2)Si(NH t Bu)3、(NEt2)Si(NHMe)3、(NEt2)Si(NHEt)3、(NEt2)Si(NH n Pr)3、(NEt2)Si(NH i Pr)3、(NEt2)Si(NH n Bu)3、(NEt2)Si(NH i Bu)3、(NEt2)Si(NH t Bu)3, (N n Pr2)Si(NHMe)3、(N n Pr2)Si(NHEt)3、(N n Pr2)Si(NH n Pr)3, (N n Pr2)Si(NH i Pr)3, (N n Pr2)Si(NH n Bu)3, (N n Pr2)Si(NH i Bu)3, (N n Pr2)Si(NH t Bu)3, (N i Pr2)Si(NHMe)3、(N i Pr2)Si(NHEt)3、(N i Pr2)Si(NH n Pr)3, (N i Pr2)Si(NH i Pr)3, (N i Pr2)Si(NH n Bu)3, (N i Pr2)Si(NH i Bu)3, (N i Pr2)Si(NH t Bu)3, (N n Bu2)Si(NHMe)3、(N n Bu2)Si(NHET)3、(N n Bu2)Si(NH n Pr)3, (N n Bu2)Si(NH i Pr)3, (N n Bu2)Si(NH n Bu)3, (Nn Bu2)Si(NH i Bu)3, (N n Bu2)Si(NH t Bu)3, (N i Bu2)Si(NHMe)3、(N i Bu2)Si(NHET)3、(N i Bu2)Si(NH n Pr)3, (N i Bu2)Si(NH i Pr)3, (N i Bu2)Si(NH n Bu)3, (N i Bu2)Si(NH i Bu)3, (N i Bu2)Si(NH t Bu)3, (N t Bu2)Si(NHMe)3、(N t Bu2)Si(NHET)3、(N t Bu2)Si(NH n Pr)3, (N t Bu2)Si(NH i Pr)3, (N t Bu2)Si(NH n Bu)3, (N t Bu2)Si(NH i Bu)3, (N t Bu2)Si(NH t Bu)3, (NH2)2Si(NHMe)2, (NH2)2Si(NHEt)2, (NH2)2Si(NH n Pr)2、(NH2)2Si(NH i Pr)2、(NH2)2Si(NH n Bu)2、(NH2)2Si(NH i Bu)2、(NH2)2Si(NH t Bu)2、(NMe2)2Si(NHMe)2、(NMe2)2Si(NHEt)2、(NMe2)2Si(NH n Pr)2、(NMe2)2Si(NH i Pr)2、(NMe2)2Si(NH n Bu)2、(NMe2)2Si(NH i Bu)2、(NMe2)2Si(NH tBu)2、(NEt2)2Si(NHMe)2、(NEt2)2Si(NHEt)2、(NEt2)2Si(NH n Pr)2、(NEt2)2Si(NH i Pr)2、(NEt2)2Si(NH n Bu)2、(NEt2)2Si(NH i Bu)2、(NEt2)2Si(NH t Bu)2, (N n Pr2)2Si(NHMe)2、(N n Pr2)2Si(NHEt)2、(N n Pr2)2Si(NH n Pr)2、(N n Pr2)2Si(NH i Pr)2、(N n Pr2)2Si(NH n Bu)2, (N n Pr2)2Si(NH i Bu)2, (N n Pr2)2Si(NH t Bu)2, (N i Pr2)2Si(NHMe)2、(N i Pr2)2Si(NHEt)2、(N i Pr2)2Si(NH n Pr)2、(N i Pr2)2Si(NH i Pr)2、(N i Pr2)2Si(NH n Bu)2, (N i Pr2)2Si(NH i Bu)2, (N i Pr2)2Si(NH t Bu)2, (N n Bu2)2Si(NHMe)2、(N n Bu2)2Si(NHEt)2、(N n Bu2)2Si(NH n Pr)2、(N n Bu2)2Si(NH i Pr)2、(N n Bu2)2Si(NH n Bu)2, (N n Bu2)2Si(NH i Bu)2, (N n Bu2)2Si(NHt Bu)2, (N i Bu2)2Si(NHMe)2、(N i Bu2)2Si(NHEt)2、(N i Bu2)2Si(NH n Pr)2、(N i Bu2)2Si(NH i Pr)2、(N i Bu2)2Si(NH n Bu)2, (N i Bu2)2Si(NH i Bu)2, (N i Bu2)2Si(NH t Bu)2, (N t Bu2)2Si(NHMe)2、(N t Bu2)2Si(NHEt)2、(N t Bu2)2Si(NH n Pr)2、(N t Bu2)2Si(NH i Pr)2、(N t Bu2)2Si(NH n Bu)2, (N t Bu2)2Si(NH i Bu)2, (N t Bu2)2Si(NH t Bu)2、Si(HNCH2CH2NH)2、Si(MeNCH2CH2NMe)2、Si(EtNCH2CH2NEt)2、Si( n PrNCH2CH2N n Pr)2、Si( i PrNCH2CH2N i Pr)2、Si( n BuNCH2CH2N n Bu)2、Si( i BuNCH2CH2N i Bu)2、Si( t BuNCH2CH2N t Bu)2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNCHCHNEt)2、Si( n PrNCHCHN n Pr)2、Si( i PrNCHCHN i Pr)2、Si( n BuNCHCHNn Bu)2、Si( i This is it. i Bu)2、Si( t This is it. t Bu)2、(HNCHCHNH)Si(HNCH2CH2NH)、(MeNCHCHNMe)Si(MeNCH2CH2NMe)、(EtNCHCHNEt)Si(EtNCH2CH2NEt)、( n PrNCHCHN n Pr)Si( n PrNCH2CH2N n Pr)、( i PrNCHCHN i Pr)Si( i PrNCH2CH2N i Pr)、( n This is it. n Bu(Si( n This is CH2CH2N. n This)、( i This is it. i Bu(Si( i This is CH2CH2N. i This) 、( t This is it. t Bu(Si( t This is CH2CH2N. t This)、(NH t Bu)2Si(HNCH2CH2NH)、(NH t Bu)2Si(MeNCH2CH2NMe)、(NH t Bu)2Si(EtNCH2CH2NEt) 、(NH t This is)2Si( n PrNCH2CH2N n Pr)、(NH t This is)2Si( i PrNCH2CH2N i Pr)、(NH t This is)2Si( n This is CH2CH2N. n This)、 (NH t This is)2Si( i This is CH2CH2N. i This)、(NH t This is)2Si( tBuNCH2CH2N t Bu), (NH t Bu)2Si(HNCHCHNH) 、(NH t Bu)2Si(MeNCHCHNMe) 、 (NH t Bu)2Si(EtNCHCHNEt) 、(NH t Bu)2Si( n PrNCHCHN n Pr), (NH t Bu)2Si( i PrNCHCHN i Pr), (NH t Bu)2Si( n BuNCHCHN n Bu), (NH t Bu)2Si( i BuNCHCHN i Bu), (NH t Bu)2Si( t BuNCHCHN t Bu), ( i PrNCH2CH2N i Pr)Si(NHMe)2 、( i PrNCH2CH2N i Pr)Si(NHEt)2 、( i PrNCH2CH2N i Pr)Si(NH n Pr)2 、( i PrNCH2CH2N i Pr)Si(NH i Pr)2 、 ( i PrNCH2CH2N i Pr)Si(NH n Bu)2、( i PrNCH2CH2N i Pr)Si(NH i Bu)2 、 ( i PrNCH2CH2N i Pr)Si(NH t Bu)2 、( i PrNCHCHN i Pr)Si(NHMe)2、 ( i PrNCHCHN i Pr)Si(NHEt)2 、( i PrNCHCHNi Pr)Si(NH n Pr)2、 ( i PrNCHCHN i Pr)Si(NH i Pr)2、( i PrNCHCHN i Pr)Si(NH n Bu)2、 ( i PrNCHCHN i Pr)Si(NH i Bu)2 and ( i PrNCHCHN i Pr)Si(NH t It may be one or more of Bu2, but is not limited to this.

[0116] The n Pr represents n-propyl. i Pr represents isopropyl. n Bu represents n-butyl. i Bu represents isobutyl. t Bu represents tert-butyl.

[0117] In a preferred embodiment, the thin film precursor compound may include one or more selected from TiCl4, Ti(CpMe5)(OMe)3, Ti(CpMe3)(OMe)3, Ti(OMe)4, Ti(OEt)4, Ti(OtBu)4, Ti(CpMe)(OiPr)3, TTIP(Ti(OiPr)4, TDMAT(Ti(NMe2)4), Ti(CpMe){N(Me2)3}, Pt, Ru, Ir, PtO, PtO2, RuO2, IrO2, SrRuO3, BaRuO3, and CaRuO3. In this case, the desired effect of the present invention can be fully achieved.

[0118] The titanium tetrahalide can be used as a metal precursor for compositions used in thin film formation. As an example, the titanium tetrahalide can be one or more selected from TiF4, TiCl4, TiBr4, and TiI4; for example, TiCl4 is preferred in terms of economy, but is not limited thereto.

[0119] As an example, the titanium tetrahalide exhibits excellent thermal stability, does not decompose at room temperature, and exists in a liquid state. Therefore, it is suitable as a precursor for atomic layer deposition (ALD) to deposit thin films.

[0120] As an example, the film precursor compound can be mixed with a nonpolar solvent (except for those overlapping with the hydrocarbon) and added into the chamber, which has the advantage of making it easy to adjust the viscosity and vapor pressure of the film precursor compound.

[0121] The nonpolar solvent is preferably selected from one or more alkanes and cycloalkanes. In this case, it has the advantages of containing organic solvents with low reactivity and solubility and easy water management, and improving step coverage even when the deposition temperature is increased during film formation.

[0122] As a more preferred example, the nonpolar solvent may include C1-C10 alkanes or C3-C10 cycloalkanes, preferably C3-C10 cycloalkanes, which have the advantages of low reactivity and solubility and easy moisture management.

[0123] In this application, C1, C3, etc., represent the number of carbon atoms.

[0124] The cycloalkanes are preferably C3 to C10 monocycloalkanes. Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, so it is suitable for vapor deposition processes, but is not limited thereto.

[0125] As an example, the solubility of the nonpolar solvent in water (at 25°C) is less than 200 mg / L, preferably 50 to 200 mg / L, and more preferably 135 to 175 mg / L. Within this range, it has the advantages of low reactivity to film precursor compounds and easy moisture management.

[0126] In this application, solubility can be measured using conventional measurement methods or standards in the technical field to which this invention pertains. For example, saturated solutions can be measured using HPLC.

[0127] The content of the nonpolar solvent is preferably 5-95% by weight, more preferably 10-90% by weight, even more preferably 40-90% by weight, and most preferably 70-90% by weight, relative to the total weight of the film precursor compound and the nonpolar solvent.

[0128] When the content of the added nonpolar solvent exceeds the upper limit, it will induce impurities, leading to an increase in resistance and impurity values ​​in the thin film. When the content of the added organic solvent is less than the lower limit, the improvement effect of the added solvent on step coverage and the reduction effect of impurities such as chloride (Cl) ions are not significant.

[0129] Preferably, the compound represented by chemical formula 2 or the conductive compound can be a liquid at room temperature (22°C) with a density of 0.8–2.5 g / cm³. 3 Or 0.8~1.5g / cm 3The vapor pressure (20°C) can be 0.1–300 mmHg or 1–300 mmHg. Within this range, it has excellent effects on step coverage, film thickness uniformity, and film quality improvement.

[0130] More preferably, the density of the compound represented by chemical formula 2 or the conductive compound can be 0.75 to 2.0 g / cm³. 3 Or 0.8~1.8g / cm 3 The vapor pressure (20℃) can be 1~260mmHg. Within this range, it has excellent effects on step coverage, film thickness uniformity and film quality improvement.

[0131] The ratio of the auxiliary precursor to the intracavitary loading (mg / cycle) of the film precursor compound is preferably 1:0.1 to 1:20, more preferably 1:0.2 to 1:15, even more preferably 1:0.5 to 1:12, and even more preferably 1:0.7 to 1:10. Within this range, the improvement in step coverage and the reduction in process byproducts are significant.

[0132] The precursor composition consisting of the auxiliary precursor and the thin film precursor compound is preferably used in atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma-enhanced chemical vapor deposition (PECVD) processes. In this case, it has the advantages of significantly reducing process by-products, excellent step coverage, improved film density, and better electrical properties of the film.

[0133] The thin film formation method of the present invention includes the step of injecting the precursor composition into a chamber and adsorbing it onto the surface of a loaded substrate. At this time, side reactions can be suppressed and the thin film growth rate can be adjusted during the formation of the thin film, reducing process by-products in the thin film to reduce corrosion and degradation, and improving the crystallinity of the thin film. Thus, even when forming a thin film on a substrate with a complex structure, the step coverage and electrical properties of the thin film are significantly improved.

[0134] In the step of adsorbing the precursor composition onto the surface of the substrate, the feeding time of the precursor composition onto the surface of the substrate per cycle is preferably 0.01 to 10 seconds, more preferably 0.02 to 5 seconds, even more preferably 0.04 to 3 seconds, and even more preferably 0.05 to 2 seconds. Within this range, it has the advantages of low film growth rate, excellent step coverage, and good economy.

[0135] In this application, the feeding time of the precursor composition is based on a chamber volume of 15 to 20 L and a flow rate of 0.5 to 100 mg / s, and more specifically, on a chamber volume of 18 L and a flow rate of 1 to 25 mg / s.

[0136] In a preferred embodiment, the thin film formation method may include the following steps: step i), vaporizing the precursor composition and adsorbing it onto the surface of a substrate loaded in a chamber; step ii), performing a first purging of the chamber using a purge gas; step iii), supplying a reactant gas into the chamber; and step iv), performing a second purging of the chamber using a purge gas. Steps i) to iv) can then be repeated as a unit cycle until a thin film of the desired thickness is obtained. When the auxiliary precursor of the present invention is introduced together with the thin film precursor compound and adsorbed onto the substrate within one cycle, process byproducts are effectively removed even at low temperatures, thus providing the advantages of improved thin film resistivity and significantly improved step coverage.

[0137] As a preferred embodiment, the thin film formation method of the present invention can feed the auxiliary precursor and the thin film precursor compound of the present invention together in one cycle and adsorb them onto the substrate. At this time, even when depositing the thin film at low temperature, the thin film growth rate can be appropriately reduced, thereby significantly reducing process by-products and significantly improving step coverage. It can also increase the crystallinity of the thin film to improve the resistivity of the thin film. Moreover, even when applied to semiconductor devices with large aspect ratios, it can significantly improve the thickness uniformity of the thin film, thereby ensuring the reliability of the semiconductor device.

[0138] As an example, in the thin film formation method, when the auxiliary precursor is adsorbed while depositing the thin film precursor compound, the process can be repeated 1 to 99,999 times per unit cycle as needed, preferably 10 to 10,000 times per unit cycle, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the thickness of the target thin film can be obtained and the property improvement effect, including resistivity, that is intended to be achieved by the present invention can be fully realized.

[0139] Furthermore, as shown in the comparative examples described later, when the auxiliary precursor is adsorbed before or after the deposition of the thin film precursor compound, the property improvement effect, including resistivity, that is achieved when the auxiliary precursor and the thin film precursor compound are simultaneously introduced and deposited cannot be realized.

[0140] When the auxiliary precursor and the film precursor compound are adsorbed together onto the substrate, in the step of purging the unadsorbed precursor composition, the amount of purge gas introduced into the chamber is sufficient to remove the unadsorbed precursor composition. For example, this can be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed precursor composition can be sufficiently removed to uniformly form the film and prevent film degradation. The amounts of purge gas and precursor composition introduced are based on one cycle, and the volume of the precursor composition represents the volume of vaporized film precursor composition vapor.

[0141] As a specific example, when the precursor composition is injected at a flow rate of 1.66 mL / s and an injection time of 0.5 seconds (sec) (per cycle), and in the step of purging the unadsorbed precursor composition, the amount of purge gas injected is 602 times the amount of the film precursor composition injected.

[0142] Furthermore, as an example, in the purging step immediately following the reaction gas supply step, the amount of purging gas introduced into the chamber can be 10 to 10,000 times the volume of the reaction gas introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, based on the volume of the reaction gas introduced. Within this range, the desired effect can be sufficiently achieved. The amounts of purging gas and reaction gas introduced are based on one cycle.

[0143] Preferably, the film precursor composition and film precursor compound can be moved into the ALD chamber, CVD chamber, PEALD chamber or PECVD chamber via VFC, DLI or LDS. More preferably, they can be moved into the ALD chamber via LDS.

[0144] The ratio of the auxiliary precursor to the film precursor compound in the chamber (mg / cycle) of the precursor composition is preferably 1:0.1 to 1:20, more preferably 1:0.2 to 1:15, even more preferably 1:0.5 to 1:12, and even more preferably 1:0.7 to 1:10. Within this range, the improvement in step coverage and the reduction in process byproducts are significant.

[0145] As an example, when the thin film formation method uses the precursor composition, the resistivity (μΩ·cm) improvement calculated by Formula 1 is -51% or less, preferably -51% to -10%, within which step coverage, resistivity characteristics and film thickness uniformity are excellent.

[0146] Mathematical formula 1:

[0147] Resistivity improvement (%) = [(Resistivity with auxiliary precursor - Resistivity without auxiliary precursor) / Resistivity without auxiliary precursor] × 100

[0148] In Equation 1, the degree of resistivity improvement with and without the auxiliary precursor represents the respective conductivity characteristics, i.e., resistivity (μΩ·cm). As an example, the resistivity can be obtained based on the thickness value of the thin film after the sheet resistance is measured by the four-point probe method.

[0149] In Formula 1, "using an auxiliary precursor" means that the auxiliary precursor and the thin film precursor compound are adsorbed onto the substrate together in the thin film deposition process to manufacture the thin film, while "not using an auxiliary precursor" means that the thin film precursor compound is adsorbed onto the substrate in the thin film deposition process instead of using an auxiliary precursor to manufacture the thin film.

[0150] Regarding the aforementioned thin film formation method, Based on the film thickness, the residual halogen intensity (c / s) in the film measured by XPS can be 100,000 or less, preferably 70,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less. As a preferred embodiment, it can be 5,000 or less, more preferably 1,000 to 4,000, even more preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and deterioration is excellent.

[0151] In this application, the purging rate can be 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), preferably 2,000 to 30,000 sccm, more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is appropriately controlled, and deposition is performed in an atomic mono-layer or similar manner, thus having an advantageous effect on film quality.

[0152] The ALD (Atomic Layer Deposition) process is highly advantageous for manufacturing integrated circuits (ICs) that require high aspect ratios, especially due to its self-limiting thin film growth mechanism, which provides advantages such as excellent conformality, uniformity, and precise thickness control.

[0153] As an example, the thin film formation method can be carried out at a deposition temperature in the range of 50 to 800°C, preferably in the range of 200 to 700°C, more preferably in the range of 250 to 500°C, and even more preferably in the range of 250 to 600°C. Within this range, it has the effect of exhibiting the characteristics of the ALD process and growing a thin film with preferred film quality.

[0154] As an example, the thin film formation method can be carried out at a deposition pressure in the range of 0.01 to 20 Torr, preferably in the range of 0.1 to 20 Torr, more preferably in the range of 0.1 to 10 Torr, and most preferably in the range of 0.1 to 7 Torr, within which a thin film with uniform thickness is obtained.

[0155] In this application, the deposition temperature and deposition pressure can be the measured temperature and pressure formed in the deposition chamber, or the measured temperature and pressure applied to the substrate in the deposition chamber.

[0156] Preferably, the thin film formation method may include the following steps: heating the temperature inside the chamber to the deposition temperature before introducing the precursor composition into the chamber; and / or injecting an inert gas into the chamber for purging before introducing the precursor composition into the chamber.

[0157] Additionally, as a thin film manufacturing apparatus for implementing the aforementioned thin film manufacturing method, the thin film manufacturing apparatus of the present invention may include: an ALD chamber; a first vaporizer for vaporizing an auxiliary precursor; a first transfer unit for transferring the vaporized auxiliary precursor into the ALD chamber; a second vaporizer for vaporizing a thin film precursor compound; and a second transfer unit for transferring the vaporized thin film precursor compound into the ALD chamber.

[0158] Additionally, in this invention, the thin film manufacturing apparatus may include a mixing unit for mixing the vaporized auxiliary precursor with the vaporized thin film precursor compound to premix the precursor composition before transferring it into the chamber.

[0159] The vaporizer, transfer unit, or mixing unit can be any vaporizer, transfer unit, or mixing unit that is conventionally used in the technical field to which this invention pertains.

[0160] As a specific example, the thin film formation method using the ALD process described above is as follows.

[0161] First, the substrate on which the thin film is to be formed is placed in a deposition chamber where atomic layer deposition can be performed.

[0162] The substrate may include a silicon substrate, a silicon oxide semiconductor substrate, or other semiconductor substrates.

[0163] The substrate may further have a conductive layer or an insulating layer formed on its upper part.

[0164] Prepare the above-mentioned auxiliary precursor and film precursor compounds, or mixtures thereof with nonpolar solvents, to deposit a film on a substrate placed in the deposition chamber.

[0165] Subsequently, the prepared auxiliary precursor, film precursor compound, or mixture of its nonpolar solvent (film forming composition) is injected into a vaporizer to convert it into a vapor phase and then transferred to the deposition chamber for adsorption onto the substrate. Alternatively, the film forming composition is prepared in advance and then converted into a vapor phase using a vaporizer and transferred to the deposition chamber for adsorption onto the substrate. Next, purging is performed to remove the unadsorbed precursor composition (film forming composition).

[0166] According to one embodiment of the present invention, since an auxiliary precursor that does not react with the film precursor compound is used, most of the auxiliary precursor can be removed during purging.

[0167] In this application, as an example, the auxiliary precursor and thin film precursor compound (the composition for thin film formation) can be transferred to the deposition chamber by means of a gas flow control (VFC) method that uses a mass flow controller (MFC) method to transfer volatile gases or a liquid delivery system (LDS) method that uses a liquid mass flow controller (LMFC) method to transfer liquids, with the LDS method being preferred.

[0168] At this time, the carrier gas or dilution gas used to transfer the auxiliary precursor and thin film precursor compound to the substrate can be one or a mixture of two or more of argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0169] In this application, as an example, the purging gas may be an inert gas, preferably the carrier gas or dilution gas.

[0170] Next, a reaction gas is supplied. The reaction gas can be any reaction gas conventionally used in the technical field of this invention, preferably including a reducing agent, a nitriding agent, or an oxidizing agent. The reducing agent reacts with the thin film precursor compound adsorbed on the substrate to form a metal thin film, the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

[0171] Preferably, the reducing agent can be ammonia (NH3) or hydrogen (H2), the nitriding agent can be nitrogen (N2), hydrazine (N2H4), or a mixture of nitrogen and hydrogen, and the oxidizing agent can be one or more selected from H2O, H2O2, O2, O3, and N2O.

[0172] The next step involves purging the unreacted residual reaction gases with an inert gas. This removes not only the reaction gases but also the generated byproducts.

[0173] As described above, as an example, the thin film forming method may take the steps of adsorbing the precursor composition onto the substrate, purging the unadsorbed precursor composition, supplying the reactive gas, and purging the residual reactive gas as a unit cycle, and repeat the unit cycle to form a thin film of the desired thickness.

[0174] As an example, the unit cycle can be repeated 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, it has the effect of better exhibiting the characteristics of the target thin film.

[0175] The present invention also provides a semiconductor substrate, which is formed by the thin film forming method of the present application, thereby achieving excellent step coverage, thickness uniformity, resistivity characteristics, density, and electrical properties of the thin film.

[0176] Preferably, the thickness of the thin film manufactured above is 30 nm or less, with a film thickness of 10 nm as a reference, the resistivity is 5 to 400 μΩ·cm, the halogen content is 10,000 ppm or less, and the step coverage is 80% or more. Within this range, it has excellent performance as an anti-diffusion film and reduces corrosion of metal wiring materials, but is not limited thereto.

[0177] As an example, the thickness of the film can be 1 to 30 nm, preferably 2 to 27 nm, more preferably 3 to 25 nm, and even more preferably 5 to 23 nm. Within this range, it has excellent film properties.

[0178] As an example, based on a film thickness of 10 nm, the resistivity of the film can be 5 to 400 μΩ·cm, preferably 5 to 360 μΩ·cm, within which the film exhibits excellent thin film properties.

[0179] The halogen content of the thin film is preferably 10,000 ppm or less, or 1 to 8,000 ppm, more preferably 1 to 5,000 ppm, and even more preferably 1 to 1,000 ppm. Within this range, it has the effects of excellent thin film properties and reduced corrosion of the metal wiring material. Among them, as an example, the halogen remaining in the thin film can be Cl2, Cl or Cl - , and the lower the halogen residue in the thin film, the better the film quality.

[0180] As an example, the step coverage of the thin film can be 80% or more, preferably 90% or more, and more preferably 95% or more. Within this range, the advantage is that even if the thin film structure is complex, it is easy to deposit on the substrate, so it can be applied to next-generation semiconductor devices.

[0181] As an example, the thin film manufactured above may include one or two selected from titanium nitride film (Ti x N y , where 0 < x ≤ 1.2, 0 < y ≤ 1.2, preferably 0.8 ≤ x ≤ 1, 0.8 ≤ y ≤ 1, and more preferably both are 1) and titanium oxide film (TiO2). Excellent includes titanium nitride film. At this time, it has the advantages of being suitable for use as an anti-diffusion film, an etch stop film or a wiring (electrode) of a semiconductor element.

[0182] As an example, the thin film may have a multi-layer structure of two or three layers as needed. As a specific example, the multi-layer film with a two-layer structure can be a lower layer film - middle layer film structure. As a specific example, the multi-layer film with a three-layer structure can be a lower layer film - middle layer film - upper layer film structure.

[0183] As an example, the lower layer film can be a dielectric film and may contain one or more selected from SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, LaAlO3, BaZrO3, SrZrO3, SrTiO3, BaTiO3, Si3N4, SrO, La2O3, Ta2O5, BaO, TiO2.

[0184] As an example, the middle layer film may contain Ti x N y , preferably TiN.

[0185] As an example, the upper layer film may contain one or more selected from W and Mo.

[0186] The following preferred embodiments and accompanying drawings are provided to aid in understanding the present invention. The embodiments and drawings are merely examples of the present invention. Those skilled in the art will understand that various changes and modifications can be made within the scope and technical concept of the present invention, and these changes and modifications fall within the scope of the appended claims.

[0187] Example

[0188] Examples 1 to 6, Comparative Examples 1 to 5

[0189] <Reactivity Testing of Auxiliary Precursors and Thin Film Precursor Compounds>

[0190] The reactivity of the auxiliary precursors to be used in Examples 1 to 6 and Comparative Examples 1 to 5 with the film precursor compounds was tested.

[0191] Select the combinations shown in Table 1 as the reactivity test subjects.

[0192] As a specific example, H-NMR was measured before the thin film precursor compound shown in Table 1 was mixed with the auxiliary precursor, and then H-NMR was measured again after mixing at a 1:1 molar ratio and storing in a pressure vessel for 1 hour.

[0193] By comparing the H-NMR spectra before and after mixing, the newly generated NMR peaks are identified as impurities, and the integral value at the top of the generated NMR peak is defined as the impurity content.

[0194] When the percentage of the impurity content is less than 0.1%, it is evaluated as no reaction has occurred, and when it is greater than 0.1%, it is evaluated as a reaction has occurred. The results are shown in Table 1.

[0195] As a specific example, the evaluation method for 1-iodobutane, which was evaluated as unreacted in Table 1, is described in detail below.

[0196] First, such as Figure 1 As shown, compared to the H-NMR measured alone for 1-iodobutane (corresponding to...), Figure 1 The upper part of the image shows the 1H-NMR spectrum obtained after mixing 1-iodobutane and TiCl4 at a 1:1 molar ratio and placing the mixture in a pressurized container for 1 hour. Figure 1 The top of the newly generated peak in the lower part of the figure is considered an impurity. Based on its content, the calculated result is 0.03%, which is lower than the benchmark value of 0.1%. Therefore, it is evaluated as no reaction has occurred.

[0197] The same evaluation process was repeated for the other substances, and the reactions that occurred and those that did not were recorded.

[0198] Table 1:

[0199]

[0200] As shown in Table 1, it was confirmed that among the sixteen proposed combinations, the seven combinations that mix the auxiliary precursor with the electron acceptor terminal group with the thin film precursor compound have a reactivity of less than 0.1%, demonstrating reaction stability.

[0201] Examples 1 to 6

[0202] The compounds listed in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as a thin film precursor compound. The prepared auxiliary and thin film precursor compounds were separately loaded into canisters and fed into a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. After the auxiliary and thin film precursor compounds, vaporized in the vaporizer, were introduced into the deposition chamber containing the substrate at a 1:1 ratio for 1 second, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr.

[0203] Next, ammonia gas, acting as a reactive gas, is introduced into the reaction chamber at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate to which the metal thin film is to be formed is heated to the temperature shown in Table 2. This process is repeated 200–400 times to form a TiN thin film with a thickness of 10 nm as a self-limiting atomic layer.

[0204] Comparative Examples 1 and 2

[0205] The compounds listed in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as the thin film precursor compound. After the prepared auxiliary precursors were loaded into a container, they were supplied at room temperature to a vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min. After the auxiliary precursor, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 1 second, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr.

[0206] Next, the prepared TiCl4 was placed in a separate container and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. One second after the TiCl4, vaporized in the vaporizer, was introduced into the deposition chamber, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0207] Next, ammonia gas, acting as a reactive gas, is introduced into the reaction chamber at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate to which the metal thin film is to be formed is heated to the temperature shown in Table 2. This process is repeated 200–400 times to form a TiN thin film with a thickness of 10 nm as a self-limiting atomic layer.

[0208] Comparative Example 3

[0209] Prepare the compounds listed in Table 1 as auxiliary precursors, and prepare TiCl4 as a thin film precursor compound.

[0210] After the prepared TiCl4 was placed in a separate container, it was supplied at room temperature to a separate vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min. One second after the TiCl4, vaporized in the vaporizer, was introduced into the deposition chamber, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr.

[0211] Next, the prepared auxiliary precursor was loaded into a container and supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. After the auxiliary precursor, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 1 second, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0212] Next, ammonia gas, acting as a reactive gas, is introduced into the reaction chamber at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate to which the metal thin film is to be formed is heated to the temperature shown in Table 2. This process is repeated 200–400 times to form a TiN thin film with a thickness of 10 nm as a self-limiting atomic layer.

[0213] Comparative Example 4

[0214] The compounds listed in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as the thin film precursor compound. After the prepared auxiliary precursors were loaded into a container, they were supplied at room temperature to a vaporizer heated to 150°C using a Liquid Mass Flow Controller (LMFC) at a flow rate of 0.05 g / min. After the auxiliary precursor, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 1 second, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure in the reaction chamber was controlled at 2.5 Torr.

[0215] Next, the prepared TiCl4 was placed in a separate container and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.05 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. One second after the TiCl4, vaporized in the vaporizer, was introduced into the deposition chamber, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0216] Next, ammonia gas, acting as a reactive gas, is introduced into the reaction chamber at 1000 sccm for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate to which the metal thin film is to be formed is heated to the temperature shown in Table 2. This process is repeated 200–400 times to form a TiN thin film with a thickness of 10 nm as a self-limiting atomic layer.

[0217] Comparative Example 5

[0218] Except that the auxiliary precursor used in Example 1 was replaced with the compound described in Table 1, the same process as in Example 1 was repeated to form a TiN thin film.

[0219] Experimental Example

[0220] 1) Sedimentary assessment (sedimentation rate per cycle)

[0221] For the fabricated thin film, the thickness of the thin film is measured using an ellipsometer, and then divided by the number of cycles to calculate the thickness of the thin film deposited in each cycle to evaluate the deposition rate. The results are shown in Table 2. An ellipsometer is a device that can measure optical properties such as the thickness and refractive index of a thin film by utilizing the polarization characteristics of light.

[0222] 2) Thin film resistance evaluation (resistivity)

[0223] After measuring the surface resistance of the fabricated thin film using the four-point probe method to determine the surface resistance, the resistivity value is calculated based on the thickness of the thin film.

[0224] The improvement in resistivity (μΩ·cm) is calculated according to mathematical formula 1.

[0225] Mathematical formula 1:

[0226] Resistivity improvement (%) = [(Resistivity with precursor composition - Resistivity without auxiliary precursor) / Resistivity without auxiliary precursor] × 100

[0227] Table 2:

[0228]

[0229] *Control group: Measurements for TiN films fabricated without the use of auxiliary precursors.

[0230] As shown in Table 2, compared with using an auxiliary precursor as a growth inhibitor before the film precursor compound (Comparative Examples 1, 2, 4), using an auxiliary precursor as a growth active substance after the film precursor compound (Comparative Example 3), or replacing the auxiliary precursor with a type that is reactive with the film precursor compound (Comparative Example 5), the present invention provides the same or similar deposition rate when using 1-iodobutane, 2-iodobutane, 2-iodo-2-methylpropane, 2-iodobutane, iodocyclohexane, or 3-iodopentane as auxiliary precursors together with the film precursor compound (Examples 1 to 6), and the resistivity is reduced to 160 to 358 μΩ·cm. In particular, the resistivity characteristics are significantly reduced by -51% to -10% compared with the control group that did not use auxiliary precursors. Therefore, it can be confirmed that the film growth rate is appropriately controlled, thereby improving the electrical properties.

[0231] Specifically, it was confirmed that in Comparative Example 1, where 1-iodobutane was used as an auxiliary precursor but as a growth inhibitor, the resistivity was 1224 μΩ·cm, which was significantly higher than the 518 μΩ·cm of the control group that did not use the auxiliary precursor.

[0232] Furthermore, in Comparative Example 2, where 2-iodobutane was used as a growth inhibitor, the resistivity was 320 μΩ·cm, which was not significantly different from the 329 μΩ·cm of the control group without the auxiliary precursor. In Comparative Example 3, where 2-iodobutane was used as a growth active agent, the resistivity was 364 μΩ·cm, which was also not significantly different from the 329 μΩ·cm of the control group without the auxiliary precursor. Therefore, it can be confirmed that no improvement in the electrical properties of the thin film was observed.

[0233] Furthermore, it has been confirmed that it does not react with the film precursor compound at room temperature. However, in Comparative Example 4, where an auxiliary precursor without the electron acceptor end group unique to this invention was used as a growth inhibitor, no improvement in the electrical properties of the film was observed.

[0234] Furthermore, it was confirmed that in Comparative Example 5, in which an auxiliary precursor that does not react with the film precursor compound was used together with the film precursor compound, no improvement in the electrical properties of the film was observed.

[0235] 3) Impurity reduction characteristics

[0236] X-ray photoelectron spectroscopy (XPS) analysis was performed on titanium (Ti), nitrogen (N), chlorine (Cl), carbon (C), and oxygen (O) to compare the reduction characteristics of impurities, i.e. process byproducts, in the fabricated 10 nm thick film. The results are shown in Table 3.

[0237] Table 3:

[0238]

[0239] As shown in Table 3, it can be confirmed that when the auxiliary precursor of the present invention is used simultaneously with the film precursor compound (Example 6), compared with when an auxiliary precursor that is unsuitable in terms of reactivity with the film precursor compound is simultaneously injected with the film precursor compound (Comparative Example 5), the Cl and C intensities are reduced to the order of 0.01%, thus exhibiting excellent impurity reduction characteristics. In particular, it can be confirmed that Comparative Example 5 uses an auxiliary precursor that does not react with the film precursor compound in the film deposition process, so theoretically carbon should not be detectable. However, carbon suspected to originate from the film precursor compound, purge gas, and CO and / or CO2 contained in the reaction gas is detected. However, although Example 6 of the present invention uses an auxiliary precursor as a hydrocarbon during film deposition, the carbon intensity is lower than that of Comparative Example 5, indicating that the auxiliary precursor of the present invention has excellent impurity reduction characteristics.

[0240] In particular, it was confirmed that although Comparative Example 5 incorporated a compound with a similar structure to the auxiliary precursor of the present invention into the precursor composition in the same manner as the present invention, the impurity intensity was too high compared to Example 6 or the control group (Ref.), and therefore it did not have a membrane quality improvement effect.

Claims

1. A thin film precursor composition, characterized in that, It includes auxiliary precursors of linear, branched, or cyclic alkane compounds represented by Formula 1, and thin film precursor compounds represented by Formula 2. Chemical Formula 1: A n B m X o In the chemical formula 1, A is carbon, B is hydrogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms, X is iodine (I), n is an integer from 1 to 15, o is 1, and m is 0 to 2n+1. Chemical formula 2: M x L y In the chemical formula 2, x is an integer from 1 to 3, and M is selected from Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb Among Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, y is an integer from 0 to 6, and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand composed of two or more selected from H, C, N, O, F, P, S, Cl, and Br. The auxiliary precursor is, and the auxiliary precursor is... 1 Compared to the H-NMR spectrum, the image obtained after mixing the auxiliary precursor and the film precursor compound at a 1:1 molar ratio and placing them in a pressurized container for 1 hour shows... 1 Compounds whose integral value at the top of the newly formed peak in the H-NMR spectrum is less than 0.1%.

2. The thin film precursor composition according to claim 1, characterized in that, The weight ratio of the auxiliary precursor to the film precursor compound is 1:99 to 99:

1.

3. The thin film precursor composition according to claim 1, characterized in that, The auxiliary precursor is selected from one or more of 1-iodobutane, 2-iodobutane, iodocyclohexane, 2-iodo-2-methylpropane, and 3-iodo-2,4-dimethylpentane.

4. The thin film precursor composition according to claim 1, characterized in that, The thin film precursor composition is used in atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma-enhanced chemical vapor deposition (PECVD) processes.

5. A method for forming a thin film, characterized in that, Includes the following steps: The thin film precursor composition of claim 1 is injected into the chamber and adsorbed onto the surface of the loaded substrate.

6. The thin film forming method according to claim 5, characterized in that, Includes the following steps: Step i) involves vaporizing the thin film precursor composition and adsorbing it onto the surface of the substrate loaded in the chamber; Step ii) involves first purging the interior of the chamber using purge gas; Step iii), supplying the reaction gas into the chamber; and Step iv) involves a second purging of the chamber using purging gas.

7. The thin film formation method according to claim 5, characterized in that, The thin film precursor composition is transferred to an atomic layer deposition chamber, chemical vapor deposition chamber, plasma-enhanced atomic layer deposition chamber, or plasma-enhanced chemical vapor deposition chamber via VFC, DLI, or LDS.

8. The thin film forming method according to claim 5, characterized in that, The ratio of the auxiliary precursor to the intracavitary loading (mg / cycle) of the film precursor composition is 1:0.1 to 1:

20.

9. The thin film forming method according to claim 6, characterized in that, The reactant gas is a reducing agent, a nitriding agent, or an oxidizing agent.

10. The thin film formation method according to claim 5, characterized in that, The deposition temperature of the thin film formation method is 200–700°C.

11. The thin film forming method according to claim 5, characterized in that, The thin film is an oxide film, a nitride film, or a metal film.

12. The thin film forming method according to claim 11, characterized in that, The film comprises a multilayer structure with two or three layers.

13. A semiconductor substrate, characterized in that, It is made by the thin film forming method according to claim 5.

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