Supplementary precursors, thin film precursor compositions, thin film formation methods, and semiconductor substrates produced therefrom

Abstract

The present invention relates to an auxiliary precursor, a thin film precursor composition, a method for forming a thin film using the same, and a semiconductor substrate manufactured therefrom. The present invention provides a thin film precursor composition including a compound having a predetermined structure as an auxiliary precursor, which exhibits reaction stability to a thin film precursor compound. The thin film precursor composition is used in a thin film deposition process to suppress side reactions, appropriately control the thin film growth rate, and remove process by-products in the thin film. This can significantly improve step coverage, thin film thickness uniformity, and resistivity even when a thin film is formed on a substrate having a complex structure, reduce corrosion and deterioration, improve the crystallinity of the thin film, and improve the electrical properties of the thin film.

Description

[Technical field]

[0001] The present invention relates to an auxiliary precursor, a thin film precursor composition containing the same, a method for forming a thin film using the same, and a semiconductor substrate manufactured from the same. More specifically, the present invention relates to an auxiliary precursor which suppresses side reactions and reduces the impurity concentration in the thin film, thereby preventing corrosion and deterioration of the thin film and improving the electrical properties of the thin film, and which not only improves step coverage, thin film thickness uniformity, and resistivity even when a thin film is formed on a substrate having a complex structure because the growth rate of the thin film is appropriately controlled, but also does not decompose even when mixed with a thin film precursor, a thin film precursor composition containing the same, a method for forming a thin film using the same, and a semiconductor substrate manufactured from the same. [Background technology]

[0002] As the integration density of memory and non-memory semiconductor devices increases day by day and their structures become more complex, the film quality and step coverage of thin films deposited on substrates become increasingly important.

[0003] The semiconductor thin film is made of 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 the thin film is generally used as a diffusion barrier between the silicon layer of a doped semiconductor and aluminum (Al) or copper (Cu) used as an interlayer wiring material. However, when a metal thin film such as tungsten (W) or molybdenum (Mo) is deposited on a substrate, it is used as an adhesion layer.

[0004] In order for a thin film deposited on a substrate to have excellent uniform physical properties, it is essential that the formed thin film has high step coverage. Therefore, the ALD (atomic layer deposition) process, which utilizes surface reactions, is used rather than the CVD (chemical vapor deposition) process, which mainly utilizes gas phase reactions, but there are still problems in achieving 100% step coverage.

[0005] Furthermore, a method of reducing the thin film growth rate has been proposed as one method for improving step coverage. However, when the deposition temperature is reduced to reduce the thin film growth rate, the amount of residual impurities such as carbon and chlorine in the thin film increases, resulting in a significant deterioration in film quality.

[0006] In addition, in the case of titanium tetrachloride (TiCl4) used to deposit titanium nitride (TiN), a representative metal nitride, process by-products such as chlorides remain in the thin film produced, which induces corrosion of metals such as aluminum and generates non-volatile by-products, resulting in deterioration of the film quality.

[0007] Therefore, it is necessary to develop a method for forming a thin film that allows for the formation of thin films with complex structures, has a low amount of residual impurities, and does not corrode the interlayer wiring material, as well as semiconductor substrates manufactured using this method. It is also necessary to develop an auxiliary precursor that can provide uniform thickness and step coverage even for high aspect ratios due to the increasing number of VNAND layers, such as 128 layers, 256 layers, 512 layers, etc., and that is difficult to decompose even when mixed with a thin film precursor, and has excellent effectiveness. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent Publication No. 2006-0037241 Summary of the Invention [Problem to be solved by the invention]

[0009] In order to solve the above-mentioned problems of the prior art, the present invention aims to provide an auxiliary precursor which provides a low band gap, dramatically improves the quality of thin films containing the auxiliary precursor, appropriately controls the thin film growth rate by suppressing side reactions, and prevents corrosion and deterioration by removing process by-products in the thin film. It is also an object of the present invention to provide an auxiliary precursor which not only significantly improves step coverage, thin film thickness uniformity, and resistivity characteristics even when a thin film is formed on a substrate having a complex structure, but also does not decompose even when mixed with a thin film precursor, a thin film formation method using the auxiliary precursor, and a semiconductor substrate manufactured therefrom.

[0010] Another object of the present invention is to improve the crystallinity of the thin film, thereby improving the density, resistivity, and other electrical characteristics of the thin film.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0012] In order to achieve the above object, the present invention provides an auxiliary precursor, which is a linear, branched, cyclic or aromatic compound represented by the following chemical formula 1 and is used in combination with a thin film precursor compound:

[0013] [Chemical formula 1] AnBmXoYiZj

[0014] (In the above Chemical Formula 1, A is carbon or silicon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not equal to each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers of 0 to 3.)

[0015] The auxiliary precursor is 1 The H-NMR spectrum was measured after mixing the auxiliary precursor and the thin film precursor compound in a 1:1 molar ratio and applying pressure. 1 The compound may have a peak integral of less than 0.1% for newly generated peaks in the H-NMR spectrum.

[0016] The present invention also provides a thin film precursor composition comprising: an auxiliary precursor which is a linear, branched, cyclic or aromatic compound represented by the following chemical formula 1; and a thin film precursor compound represented by the following chemical formula 2:

[0017] [Chemical formula 1] AnBmXoYiZj

[0018] (In the above Chemical Formula 1, A is carbon or silicon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not equal to each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers of 0 to 3.)

[0019] [Chemical formula 2] MxLy

[0020] (In the above Chemical Formula 2, x is an integer of 1 to 3, and M is 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, 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, where y is an integer of 0 to 6, and L is each independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0021] The auxiliary precursor and the thin film precursor compound may have a weight ratio of 1:99 to 99:1.

[0022] The auxiliary precursor may be at least one selected from the compounds represented by the following Formulas 3 to 14.

[0023] [Chemical formula 3~Chemical formula 14] JPEG0007660691000001.jpg48163

[0024] (In Chemical Formula 3 to Chemical Formula 14, the lines represent bonds, and no separate elements are shown. The points where bonds intersect represent carbon, and hydrogen atoms that satisfy the valence of the carbon are omitted.)

[0025] The thin film precursor compositions can be used in atomic layer deposition (ALD) processes, plasma enhanced atomic layer deposition (PEALD) processes, chemical vapor deposition (CVD) processes, or plasma enhanced chemical vapor deposition (PECVD) processes.

[0026] The present invention also provides a method for forming a thin film, comprising the steps of injecting the thin film precursor composition into a chamber and adsorbing the composition on a surface of a substrate loaded thereon.

[0027] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: i) vaporizing the thin film precursor composition and adsorbing it onto a surface of a substrate loaded into a chamber; ii) initially purging the interior of the chamber with a purge gas; iii) supplying a reaction gas into the chamber; and iv) secondary purging of the interior of the chamber with a purge gas.

[0028] The thin film precursor composition can be delivered inside an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber via VFC, DLI, or LDS modes.

[0029] The ratio of the amounts (mg / cycle) of the auxiliary precursor and the thin film precursor compound contained in the thin film precursor composition fed into the chamber may be 1:0.1 to 1:20.

[0030] The reactive gas may be a reducing agent, a nitriding agent or an oxidizing agent.

[0031] The thin film formation method may be carried out at a deposition temperature of 200 to 700°C.

[0032] The thin film may be an oxide film, a nitride film or a metal film.

[0033] The thin film may include a two-layer or three-layer multi-layer structure.

[0034] The present invention also provides a semiconductor substrate which is manufactured by the above-mentioned thin film forming method.

[0035] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA) or 3D NAND. Effect of the Invention

[0036] According to the present invention, it is possible to provide an auxiliary precursor that can appropriately control the thin film growth rate by controlling the deposition rate, and can improve step coverage and film quality even when a thin film is formed on a substrate having a complex structure.

[0037] In addition, since the auxiliary precursor exhibits reaction stability with respect to the thin film precursor compound, it is possible to provide an auxiliary precursor for forming a thin film, which reduces process by-products without interfering with the adsorption of the thin film precursor compound during thin film formation, prevents corrosion and deterioration, and improves the crystallinity of the thin film, thereby improving the resistivity and electrical properties of the thin film.Furthermore, it is possible to provide a thin film formation method using the same, and a semiconductor substrate manufactured from the same. [Brief description of the drawings]

[0038] [Figure 1] FIG. 1 shows the results of an experiment to confirm the decomposition of the auxiliary precursor of the present invention when it is mixed with a thin film precursor compound. The upper drawing shows the 1H-NMR spectrum of the auxiliary precursor used in Example 1 alone, and the lower drawing shows the 1H-NMR spectrum of the mixture of the auxiliary precursor and the thin film precursor compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] The present auxiliary precursor, thin film precursor composition, thin film formation method using the same, and semiconductor substrates produced therefrom will be described in detail below.

[0040] The present inventors have confirmed that when a thin film precursor compound is adsorbed on the surface of a substrate loaded inside a chamber, if an auxiliary precursor having a specific structure that does not decompose is adsorbed on the thin film precursor compound, the process by-products are reduced without hindering the adsorption of the thin film precursor compound, corrosion and deterioration are prevented, and the crystallinity of the thin film is improved, thereby significantly improving the resistivity and electrical properties of the thin film. In addition, the present inventors have confirmed that, contrary to expectations, when a composition including a thin film precursor compound and a specific auxiliary precursor is adsorbed on the surface of a substrate loaded inside a chamber, the resistivity is significantly improved compared to when the auxiliary precursor is adsorbed on the surface of a substrate loaded inside a chamber after the thin film precursor compound is first adsorbed on the surface of the substrate loaded inside the chamber, or when the auxiliary precursor is adsorbed on the surface of a substrate loaded inside the chamber before the thin film precursor compound is adsorbed on the surface of the substrate loaded inside the chamber. Based on this, the present invention has been completed by pursuing research.

[0041] In a preferred embodiment, the method for forming a thin film may include the steps of: i) vaporizing a thin film precursor composition including the auxiliary precursor and a thin film precursor mixture, and adsorbing the vaporized thin film precursor composition on a surface of a substrate loaded in a chamber; ii) primarily purging the inside of the chamber with a purge gas; iii) supplying a reaction gas into the chamber; and iv) secondly purging the inside of the chamber with a purge gas. In this case, the thin film growth rate is controlled, and even if the deposition temperature during thin film formation is high, the generated process by-products are effectively removed, improving the resistivity of the thin film and greatly improving step coverage.

[0042] In another preferred embodiment, the method for forming a thin film may include the steps of: i) vaporizing the auxiliary precursor and the thin film precursor compound, respectively, and adsorbing them onto a surface of a substrate loaded inside a chamber; ii) primarily purging the inside of the chamber with a purge gas; iii) supplying a reaction gas into the chamber; and iv) secondly purging the inside of the chamber with a purge gas. In this case, the thin film growth rate is controlled, and even if the deposition temperature during thin film formation is high, the generated process by-products are effectively removed, thereby improving the resistivity of the thin film and greatly improving step coverage.

[0043] The thin film precursor composition including the auxiliary precursor and the thin film precursor compound can be independently delivered into the chamber, preferably by a VFC method, a DLI method or an LDS method, and more preferably by an LDS method.

[0044] The thin film precursor composition comprising the auxiliary precursor and the thin film precursor compound may be preferably used in an atomic layer deposition (ALD) process, a plasma enhanced atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma enhanced chemical vapor deposition (PECVD) process, more preferably used in an atomic layer deposition (ALD) process or a plasma enhanced chemical vapor deposition (PECVD) process.

[0045] The thin film precursor compound may be a thin film precursor compound represented by the following chemical formula 2. In this case, the intended effect of the present invention is well exhibited, and there is an advantage that the resistivity of the thin film is improved.

[0046] [Chemical formula 2] MxLy

[0047] (In the above Chemical Formula 2, the x is an integer of 1 to 3, and the M is 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, 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, where y is an integer of 0 to 6, and each L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0048] In addition, the thin film precursor composition of the present invention is characterized by including an auxiliary precursor which is a linear, branched, cyclic or aromatic compound represented by the following chemical formula 1; and a thin film precursor compound represented by the following chemical formula 2. In this case, the intended effect of the present invention is well exhibited, and there is an advantage that the resistivity of the thin film is improved.

[0049] [Chemical formula 1] AnBmXoYiZj

[0050] (In the above Chemical Formula 1, A is carbon or silicon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not the same, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers of 0 to 3.)

[0051] [Chemical formula 2] MxLy

[0052] (In the above Chemical Formula 2, the x is an integer of 1 to 3, and the M is 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, 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, where y is an integer of 0 to 6, and each L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0053] The auxiliary precursor and the thin film precursor compound may have a weight ratio of 1:99 to 99:1, a weight ratio of 1:90 to 90:1, a weight ratio of 1:85 to 85:1, or a weight ratio of 1:80 to 80:1.

[0054] As an embodiment, the auxiliary precursor may be a linear, branched or cyclic compound represented by the formula 1, in which A is carbon or silicon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not the same, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are 0. In this case, the effect of the present invention is well exhibited, and there is an advantage that the resistivity is improved.

[0055] The X is a halogen element, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine, and within this range, there are advantages in reducing process by-products and providing better adhesion to the substrate. In addition, the X may be, for example, chlorine, which has the advantages of improving thin film crystallinity, suppressing side reactions, and reducing process by-products.

[0056] In the above formula 1, X may be, as another preferred example, iodine or bromine, which has the advantage of being more suitable for a process requiring low temperature deposition.

[0057] As a preferred embodiment, the auxiliary precursor may be a linear, branched or cyclic compound represented by Chemical Formula 1, in which A is carbon, B is hydrogen or an alkyl having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not the same as each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are 0. In this case, the effect of the present invention is well exhibited, and there is an advantage that the resistivity is improved.

[0058] As a preferred embodiment, the auxiliary precursor may be a linear, branched or cyclic compound represented by the formula 1, where A is carbon, B is hydrogen or an alkyl having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not equal to each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are 0. In this case, the effects of the present invention are well exhibited, and the film exhibits improved resistivity, and has the advantages of suppressing side reactions by improving thin film crystallinity and reducing process by-products.

[0059] In another preferred embodiment, the auxiliary precursor includes a hydrocarbon compound having an electron accepting end group, and the hydrocarbon compound may be a material that is not reactive with the thin film precursor compound. When the auxiliary precursor is used, the adsorption of the thin film precursor compound is not hindered, and the process by-products are reduced. Accordingly, the deposition rate is appropriately controlled to reduce the thin film growth rate, so that even when a thin film is formed on a substrate having a complex structure, the step coverage and film quality can be improved, corrosion and deterioration can be prevented, and the crystallinity of the thin film can be improved, thereby improving the resistivity and electrical properties of the thin film.

[0060] The hydrocarbon compound may be a compound having a structure in which at least one selected from the group consisting of alkanes and cycloalkanes is substituted with an electron accepting end group. In this case, there is an advantage that the reactivity and solubility are low, and moisture control is easy, while at the same time, step coverage is improved in a trench structure having a high aspect ratio when a thin film is formed.

[0061] As a more preferred example, the hydrocarbon compound may include a C1 to C10 alkane or a C3 to C10 cycloalkane, and is preferably a C3 to C10 cycloalkane, which has the advantages of low reactivity and solubility and easy moisture management.

[0062] In this description, C1, C3 etc. refer to carbon numbers.

[0063] The cycloalkane may be preferably a C3 to C10 monocycloalkane, and among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, and is therefore preferred in the vapor deposition process, but is not limited thereto.

[0064] As used herein, unless otherwise specified, "electron accepting end group" refers to a functional group that can provide improved film quality when combined with a thin film precursor compound.

[0065] The electron accepting end groups can be, by way of example, ortho-directing and para-directing deactivation groups.

[0066] The term "ortho-directing and para-directing inactivating groups" refers to inactivating groups that are directed at the ortho and para positions when a precursor compound having a benzene ring is used, unless otherwise specified.

[0067] As another example, the electron accepting end group may be an electron acceptor having an electronegativity of 2.0 to 4.0, preferably an electronegativity of 2.0 to 3.0.

[0068] Unless otherwise specified, the electronegativity may have functional groups that satisfy the range of electronegativity when a precursor compound that does not have a benzene ring is used.

[0069] The electron-accepting end group may be, for example, a halogen element, preferably fluorine, chlorine, bromine, or iodine, more preferably bromine or iodine, and within this range, there is an advantage that the effect of reducing process by-products and improving step coverage is more excellent. In addition, the X may be, for example, iodine, which is more suitable for processes requiring low-temperature deposition. In particular, the X may be iodine, which is more effective in improving the film quality of the thin film without excessively increasing the content of impurities.

[0070] The reactivity of the hydrocarbon compound with the thin film precursor compound is expressed as the impurity content (%) of less than 0.1% when the integral value of the NMR peak generated by comparing the H-NMR spectrum measured before mixing the hydrocarbon compound with the thin film precursor compound with the H-NMR spectrum measured after pressurizing a 1:1 molar mixture for 1 hour is taken as the impurity content. Therefore, when an auxiliary precursor is used, the adsorption of the thin film precursor compound is not hindered and process by-products are reduced, and the deposition rate is appropriately controlled to reduce the thin film growth rate, thereby improving step coverage and film quality even when a thin film is formed on a substrate having a complex structure. Furthermore, corrosion and deterioration are prevented, and the crystallinity of the thin film is improved, thereby improving the resistivity and electrical properties of the thin film.

[0071] Due to the above-mentioned reactivity, the auxiliary precursor has the advantage that it can easily adjust the viscosity and vapor pressure of the thin film precursor compound and does not interfere with the behavior of the thin film precursor compound.

[0072] The hydrocarbon compound exhibiting the above reactivity and containing the electron-accepting end group may be, for example, a halogen-substituted linear or branched alkane compound or cycloalkane compound.

[0073] Specific examples include 1-iodobutane, 2-iodobutane, 2-iodo-3-methylbutane, 3-iodo-2,4-dimethylpentane, cyclohexyl iodide, cyclopentyl iodide, 1-bromobutane, 2-bromobutane, 2-bromo-3-methylbutane, 3-bromo-2,4-dimethylpentane, cyclohexyl bromide, and cyclopentyl bromide. bromides, preferably 1-iodobutane and 2-iodobutane, which has the advantage of effectively protecting the substrate surface as an auxiliary precursor without interfering with the adsorption of the thin film precursor compound, and effectively removing process by-products.

[0074] As discussed above, the hydrocarbon compound may be a halogen-substituted hydrocarbon, and specific examples include compounds represented by the following formulae 3 to 14. Here, the compounds represented by formulae 3 to 14 may be selected independently or may be used in combination.

[0075] [Chemical formula 3~Chemical formula 14] JPEG0007660691000002.jpg48163

[0076] (In Chemical Formula 3 to Chemical Formula 14, the lines represent bonds, and no separate elements are shown. The points where bonds intersect represent carbon, and hydrogen atoms that satisfy the valence of the carbon are omitted.)

[0077] The auxiliary precursor is preferably used in an atomic layer deposition (ALD) process, a plasma enhanced atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma enhanced chemical vapor deposition (PECVD) process, and in this case, has the advantages of effectively protecting the substrate surface as an auxiliary precursor and effectively removing process by-products without inhibiting the adsorption of a thin film precursor compound.

[0078] The auxiliary precursor is preferably liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.7g / cm 3 The vapor pressure (20°C) is 0.1 to 300 mmHg or 1 to 300 mmHg, and the solubility in water (25°C) can be 200 mg / L or less. Within this range, there is an excellent effect on step coverage, thin film thickness uniformity, and film quality improvement.

[0079] More preferably, the auxiliary precursor has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.7g / cm 3 The vapor pressure (20°C) is 1 to 260 mmHg, and the solubility in water (25°C) can be 160 mg / L or less. Within this range, there is an excellent effect on step coverage, thin film thickness uniformity, and film quality improvement.

[0080] In yet another preferred embodiment, the method for forming a thin film of the present invention includes a step of injecting the thin film precursor composition into an ALD chamber and adsorbing it onto a surface of a loaded substrate. In this case, there are advantages in that the thin film growth rate is appropriately increased, process by-products generated during thin film formation are effectively removed, impurities in the thin film are reduced, and crystallinity is significantly improved.

[0081] The thin film forming method uses a reducing agent, a nitriding agent or an oxidizing agent as a reactive gas.

[0082] In the thin film formation method, the deposition temperature is, for example, 200 to 700°C, preferably 250 to 500°C, and specific examples are 250 to 450°C, 250 to 320°C, 380 to 420°C, or 400 to 450°C. Within this range, there is an advantage that the thin film resistivity, step coverage, etc. are greatly improved.

[0083] In addition, the thin film precursor composition of the present invention may be an auxiliary precursor which is a linear, branched, cyclic or aromatic compound represented by the following chemical formula 1; and a thin film precursor compound represented by the following chemical formula 2. In this case, the intended effect of the present invention is well exhibited, and there is an advantage in that it exhibits high resistivity characteristics.

[0084] [Chemical formula 1] AnBmXoYiZj

[0085] (A is carbon or silicon, B is hydrogen or an alkyl having 1 to 10 carbon atoms, X is at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur and fluorine, and are not equal to each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are integers of 0 to 3.)

[0086] [Chemical formula 2] MxLy

[0087] (In the above Chemical Formula 2, the x is an integer of 1 to 3, and the M is 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, 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 of 0 to 6, and each L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a combination of two or more selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0088] In the above Chemical Formula 2, M is titanium, tungsten, molybdenum, silicon, hafnium, zirconium, indium or germanium, and preferably titanium, tungsten, molybdenum or silicon.

[0089] In Formula 2, L is a halogen element, preferably fluorine, chlorine, bromine, or iodine, more preferably chlorine or bromine, and within this range, there are advantages in that the process by-products are reduced and the adhesion to the substrate is more excellent. In addition, L may be chlorine, for example, and in this case, there are advantages in that the thin film crystallinity is improved and side reactions are suppressed, thereby making the process by-products reduction effect more excellent.

[0090] The compound represented by the formula 2 is a halogen-substituted tertiary alkyl compound, and specific examples thereof include titanium tetrachloride, 2-chloro-3-methyl titanium, 2-chloro-2-methyl titanium, tetrabromo titanium, 3-bromo-3-methyl titanium, 3-bromo-3-methyl titanium, titanium tetrachloride, 2-chloro-3-methyl tungsten, 2-chloro-2-methyl tungsten, tetrabromo tungsten, 3-bromo-3-methyl tungsten, 3-bromo-3-methyl tungsten, tetrachloromolybdenum (molybdenum), 2-chloro-3-methyl molybdenum, 2-chloro-2-methyl molybdenum, tetrabromo molybdenum, 3-bromo-3-methyl molybdenum, 3-bromo-3-methyl molybdenum, tetrachloro hafnium, and at least one selected from the group consisting of tetrabromoindium, 2-chloro-3-methylhafnium, 2-chloro-2-methylhafnium, tetrabromohafnium, 3-bromo-3-methylhafnium, 3-bromo-3-methylhafnium, tetrachlorohafnium, 2-chloro-3-methylzirconium, 2-chloro-2-methylzirconium, tetrabromozirconium, 3-bromo-3-methylzirconium, 3-bromo-3-methylzirconium, tetrachloroindium, 2-chloro-3-methylindium, 2-chloro-2-methylindium, tetrabromoindium, 3-bromo-3-methylindium, and 3-bromo-3-methylindium, in which case the effect of removing process by-products is large, and the improvement of step coverage and the effect of adsorption to the substrate are excellent.

[0091] The term "conductive compound" as used herein, unless otherwise specified, refers to materials that have electron donors or acceptors and can be influenced by their structure and oxidation state of charge transfer.

[0092] Although the compound represented by Formula 2 or the conductive compound has been described by way of specific examples, the present invention is not limited thereto, and is not particularly limited as long as the compound is a thin film precursor compound generally used in ALD (atomic layer deposition).

[0093] Specific examples include at least one selected from the group consisting of metal film thin film precursor compounds, metal oxide film thin film precursor compounds, metal nitride film thin film precursor compounds, and silicon nitride film thin film precursor compounds, and the metal may preferably include at least one selected from the group consisting of tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanum group elements, actinium group elements, gallium, tantalum, zirconium, ruthenium, copper, titanium, nickel, iridium, molybdenum, platinum, ruthenium, and iridium.

[0094] The metal film precursor, metal oxide film precursor, and metal nitride film precursor may be, for example, at least one selected from the group consisting 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.

[0095] The metal oxide film precursors may be independently selected from the group consisting of PtO, PtO2, RuO2, IrO2, SrRuO3, BaRuO3, and CaRuO3, by way of example only.

[0096] Specific examples of the metal film precursor, metal oxide film precursor, and metal nitride film precursor include tetrachlorotitanium, tetrachlorogermanium, tetrachlorotin, tris(isopropyl)ethylmethylaminogermanium, tetraethoxylgermanium, tetramethyltin, tetraethyltin, bisacetylacetonatetin, trimethylaluminum, tetrakis(dimethylamino)germanium, bis(n-butylamino)germanium, tetrakis(ethylmethylamino)tin, tetrakis(dimethylamino)tin, Co2(CO)8(dicobalt The cobalt octacarbonyl), CpCo(biscyclopentadienyl cobalt), Co(CO)3(NO)(cobalt tricarbonyl nitrosyl), and CpCo(CO)2(cobalt dicarbonyl cyclopentadienyl), but is not limited thereto.

[0097] Examples of the silicon nitride film precursor include SiH4, SiCl4, SiF4, SiCl2H2, Si2Cl6, TEOS, DIPAS, BTBAS, (NH2)Si(NHMe)3, (NH2)Si(NHEt)3, and (NH2)Si(NH n Pr)3, (NH2)Si(NH i Pr)3, (NH2)Si(NH n Bu)3, (NH2)Si(NH iBu)3, (NH2)Si(NH t Bu)3, (NMe2)Si(NHMe)3, (NMe2)Si(NHEt)3, (NMe2)Si(NH n Pr)3, (NMe2)Si(NH i Pr)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 nBu2)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, (N n 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 tBu)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 t Bu)2, (NEt2)2Si(NHMe)2, (Et2)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 nBu2)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(NH t 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 This is CH2CH2N. i Bu)2, Si( t This is CH2CH2N. 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 This is it. n 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 PrNCH2CH2Nn Pr), (NH t Bu)2Si( i PrNCH2CH2N i Pr), (NH t Bu)2Si( n BuNCH2CH2N n Bu), (NH t Bu)2Si( i BuNCH2CH2N i Bu), (NH t Bu)2Si( t BuNCH2CH2N t Bu), (NH t Bu)2Si(HNCHCHNH), (NH t Bu)2Si(MeNCHCHNMe) , (NH t Bu)2Si(EtNCCHCHNEt), (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 nBu)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 PrNCHCHN i 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 Bu), but is not limited thereto.

[0098] The above n Pr stands for n-propyl. i Pr stands for iso-propyl n Bu stands for n-butyl, i Bu is isobutyl, t Bu means tert-butyl.

[0099] As a preferred embodiment, the thin film precursor compound may include at least one selected from the group consisting of 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 effects to be achieved by the present invention can be sufficiently obtained.

[0100] The titanium tetrahalide may be used as a metal precursor of a thin film-forming composition. The titanium tetrahalide may be at least one selected from the group consisting of TiF4, TiCl4, TiBr4, and TiI4, and is preferably TiCl4 from an economical viewpoint, but is not limited thereto.

[0101] For example, the titanium tetrahalide has excellent thermal stability and exists in a liquid state without being decomposed at room temperature, and therefore can be usefully used as a precursor for ALD (atomic layer deposition) to deposit a thin film.

[0102] For example, the thin film precursor compound may be mixed with a non-polar solvent (excluding those that overlap with the hydrocarbon compound) and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the thin film precursor compound can be easily adjusted.

[0103] The non-polar solvent may be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, there is an advantage that the step coverage is improved even if the deposition temperature during thin film formation is increased, while containing an organic solvent that has low reactivity and solubility and is easy to control moisture.

[0104] As a more preferred example, the non-polar solvent may include a C1 to C10 alkane or a C3 to C10 cycloalkane, and is preferably a C3 to C10 cycloalkane, which has the advantages of low reactivity and solubility and easy moisture management.

[0105] In this description, C1, C3 etc. refer to carbon numbers.

[0106] The cycloalkane may be preferably a C3 to C10 monocycloalkane, and among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, making it preferable for the vapor deposition process, but is not limited thereto.

[0107] The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less, preferably 50 to 200 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantages of low reactivity with the thin film precursor compound and easy moisture control.

[0108] In the present description, the solubility is not particularly limited as long as it is based on a measurement method or standard commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by the HPLC method.

[0109] The non-polar solvent may preferably comprise 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and even more preferably 70 to 90% by weight, based on the total weight of the thin film precursor compound and the non-polar solvent.

[0110] If the content of the non-polar solvent exceeds the upper limit, impurities are induced, increasing the number of impurities in the resistor and the thin film. If the content of the organic solvent is less than the lower limit, the effect of improving step coverage and the effect of reducing impurities such as chlorine (Cl) ions by adding the solvent are not sufficient.

[0111] Preferably, the compound represented by the chemical formula 2 or the conductive compound is liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20° C.) can be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, there are excellent effects on step coverage, thin film thickness uniformity, and film quality improvement.

[0112] More preferably, the compound represented by the chemical formula 2 or the conductive compound has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.8g / cm 3 The vapor pressure (20° C.) can be 1 to 260 mmHg, and within this range, there are effects of excellent step coverage, thin film thickness uniformity, and improved film quality.

[0113] The ratio of the amounts (mg / cycle) of the auxiliary precursor and the thin film precursor compound fed into the chamber may be 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 effect of improving step coverage and the effect of reducing process by-products are large.

[0114] The precursor composition comprising the auxiliary precursor and the thin film precursor compound is preferably used in an atomic layer deposition (ALD) process, a plasma enhanced atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma enhanced chemical vapor deposition (PECVD) process. In this case, the precursor composition has the advantages of a large reduction in process by-products, excellent step coverage, an improvement in thin film density, and excellent electrical properties of the thin film.

[0115] The method for forming a thin film of the present invention includes a step of injecting the precursor composition into a chamber and adsorbing the precursor composition onto the surface of a loaded substrate. In this case, side reactions during thin film formation can be suppressed, the thin film growth rate can be controlled, process by-products in the thin film can be reduced, corrosion and deterioration can be reduced, the crystallinity of the thin film can be improved, and even when a thin film is formed on a substrate having a complex structure, step coverage and electrical properties of the thin film can be significantly improved.

[0116] In the step of adsorbing the precursor composition onto the substrate surface, the feeding time of the precursor composition onto the substrate surface is preferably 0.01 to 10 seconds per cycle, 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, there are advantages in that the thin film growth rate is low, and step coverage and cost performance are excellent.

[0117] In this description, 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.

[0118] In a preferred embodiment, the method for forming a thin film includes the steps of i) vaporizing the precursor composition and adsorbing it on a surface of a substrate loaded in a chamber; ii) primarily purging the interior of the chamber with a purge gas; iii) supplying a reaction gas into the interior of the chamber; and iv) secondly purging the interior of the chamber with a purge gas. Here, the steps i) to iv) are regarded as a unit cycle, and the cycle can be repeated until a thin film of a desired thickness is obtained. In this manner, when the auxiliary precursor of the present invention is introduced together with a thin film precursor compound and adsorbed on a substrate in one cycle, there are advantages that even when deposition is performed at a low temperature, the generated process by-products are effectively removed, the resistivity of the thin film is improved, and step coverage is greatly improved.

[0119] In one preferred embodiment of the method for forming a thin film of the present invention, the auxiliary precursor of the present invention can be added together with a thin film precursor compound in one cycle and adsorbed onto a substrate. In this case, even if the thin film is deposited at a low temperature, the thin film growth rate can be appropriately reduced, so that process by-products can be significantly reduced and step coverage can be significantly improved. The crystallinity of the thin film can be increased and the resistivity of the thin film can be improved. Even when applied to a semiconductor device having a large aspect ratio, the thickness uniformity of the thin film can be significantly improved, ensuring the reliability of the semiconductor device.

[0120] In the thin film formation method, for example, when the auxiliary precursor is adsorbed simultaneously with deposition of the thin film precursor compound, a unit cycle can be repeated 1 to 99,999 times as necessary, and preferably the unit cycle can be repeated 10 to 10,000 times, more preferably 50 to 5,000 times, and further preferably 100 to 2,000 times. Within this range, a desired thin film thickness can be obtained, and the effect of improving physical properties including resistivity, which is intended to be achieved by the present invention, can be sufficiently obtained.

[0121] Furthermore, as shown in the comparative examples described later, when the auxiliary precursor was adsorbed before or after the deposition of the thin film precursor compound, the improvement in physical properties including resistivity, which was obtained when the auxiliary precursor and the thin film precursor compound were simultaneously added and deposited, was not obtained.

[0122] When the auxiliary precursor and the thin film precursor compound are adsorbed on the substrate together, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed precursor composition is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor composition, and may be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed precursor composition is sufficiently removed, so that a thin film is formed uniformly and deterioration of the film quality can be prevented. Here, the amounts of the purge gas and the precursor composition introduced are based on one cycle, and the volume of the precursor composition means the volume of the vaporized thin film precursor composition.

[0123] As a specific example, when the precursor composition is injected (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and in the step of purging the unadsorbed precursor composition, a purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec, the injection amount of the purge gas is 602 times the injection amount of the thin film precursor composition.

[0124] In addition, the amount of purge gas introduced into the chamber in the purging step performed immediately after the reaction gas supply step may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the reaction gas introduced into the chamber, and the desired effect can be sufficiently obtained within this range. Here, the amounts of the purge gas and reaction gas introduced are each based on one cycle.

[0125] The thin film precursor compositions and thin film precursor compounds are preferably delivered into the ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber by VFC, DLI, or LDS.

[0126] The ratio (mg / cycle) of the auxiliary precursor and the thin film precursor compound that constitute the precursor composition input into the chamber may be 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 effect of improving step coverage and the effect of reducing process by-products are large.

[0127] In the thin film formation method, when the precursor composition is used, for example, the improvement in resistivity (μΩ cm) calculated by the following mathematical formula 1 is −51% or less, and preferably −51% to −10%, and within this range, the step coverage, resistivity characteristics, and thin film thickness uniformity are excellent.

[0128] [Formula 1] Resistivity improvement rate (%) = [(resistivity when auxiliary precursor is used - resistivity when auxiliary precursor is not used) / resistivity when auxiliary precursor is not used] x 100

[0129] In Equation 1, the degree of improvement in resistivity when the auxiliary precursor is used and when it is not used means each conductive property, i.e., resistivity (μΩ cm), and the resistivity can be calculated from the thickness of the thin film after measuring the sheet resistance using a four-point probe, for example.

[0130] In Equation 1, "when an auxiliary precursor is used" refers to a case in which an auxiliary precursor and a thin film precursor compound are adsorbed together on a substrate in a thin film deposition process to produce a thin film, and "when an auxiliary precursor is not used" refers to a case in which a thin film is produced by adsorbing a thin film precursor compound on a substrate without using an auxiliary precursor in a thin film deposition process.

[0131] In the thin film formation method, the residual halogen intensity (c / s) in a reference thin film having a thickness of 100 Å, measured based on XPS, is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less, and in a preferred embodiment, is 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within such ranges, the effect of preventing corrosion and deterioration is excellent.

[0132] In the present description, the purge rate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and further preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition is performed as or close to an atomic mono-layer, which is advantageous in terms of film quality.

[0133] ALD (Atomic Layer Deposition) is highly advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and has advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin film growth mechanism.

[0134] The thin film formation method may be performed at a deposition temperature in the range of, for example, 50 to 800°C, preferably 200 to 700°C, more preferably 250 to 500°C, and even more preferably 250 to 600°C. Within this range, it is possible to realize the characteristics of the ALD process and grow a thin film with excellent film quality.

[0135] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and even more preferably at a deposition pressure in the range of 0.1 to 7 Torr. Within this range, it is effective to obtain a thin film of uniform thickness.

[0136] In this description, deposition temperature and deposition pressure may be measured at the temperature and pressure established within a deposition chamber, or may be measured at the temperature and pressure applied to a substrate within the deposition chamber.

[0137] The method for forming a thin film may preferably include the step of raising the temperature in the chamber to a deposition temperature before introducing the precursor composition into the chamber; and / or the step of purging the chamber by injecting an inert gas into the chamber before introducing the precursor composition into the chamber.

[0138] The present invention may also include a thin film production apparatus capable of implementing the thin film production method, the thin film production apparatus including an ALD chamber, a first vaporizer that vaporizes an auxiliary precursor, a first transfer means that transfers the vaporized auxiliary precursor into the ALD chamber, a second vaporizer that vaporizes a thin film precursor compound, and a second transfer means that transfers the vaporized thin film precursor compound into the ALD chamber.

[0139] In addition, the present invention provides a thin film manufacturing apparatus that includes a mixing means for mixing the vaporized auxiliary precursor and the vaporized thin film precursor compound, and the precursor composition can be mixed in advance and then transferred into the chamber.

[0140] Here, the vaporizer, the transport means, or the mixing means is not particularly limited as long as it is a vaporizer, a transport means, or a mixing means commonly used in the technical field to which the present invention pertains.

[0141] As a specific example, a method for forming a thin film using the ALD process will be described below. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0142] The substrate may include a semiconductor substrate such as a silicon substrate, silicon oxide, or the like.

[0143] The substrate may further have a conductive or insulating layer formed thereon.

[0144] To deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned auxiliary precursor and a thin film precursor compound or a mixture thereof with a non-polar solvent are each prepared.

[0145] Then, the prepared auxiliary precursor, thin film precursor compound, or a mixture of these non-polar solvents (thin film forming composition) is injected into a vaporizer, converted into a vapor state, and transferred to a deposition chamber for adsorption onto a substrate; alternatively, the thin film forming composition can be prepared in advance and converted into a vapor state using a vaporizer, transferred to a deposition chamber for adsorption onto a substrate, and then purging is performed to remove any unadsorbed precursor composition (thin film forming composition).

[0146] According to one embodiment of the present invention, since an auxiliary precursor that does not react with the thin film precursor compound is used, the auxiliary precursor can be largely removed during purging.

[0147] In the present description, the method of delivering the auxiliary precursor and thin film precursor compounds (compositions for forming thin films) to the deposition chamber may be, for example, a method of delivering a vaporized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC) or a method of delivering a liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System; LDS), and preferably, the LDS method is used.

[0148] In this case, the transport gas or dilution gas for transporting the auxiliary precursor and the thin film precursor compound onto the substrate may be one or a mixture of two or more gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0149] In the present description, the purge gas may be, for example, an inert gas, and preferably the transport gas or dilution gas.

[0150] Next, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention belongs, and may preferably include 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, and the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

[0151] Preferably, the reducing agent may be ammonia gas (NH3) or hydrogen gas (H2), the nitriding agent may be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas, and the oxidizing agent may be one or more selected from the group consisting of H2O, H2O2, O2, O3, and N2O.

[0152] Next, an inert gas is used to purge the remaining unreacted reactant gas, thereby removing not only the excess reactant gas but also any by-products that are produced.

[0153] As described above, in the thin film formation method, for example, a step of adsorbing a precursor composition on a substrate, a step of purging unadsorbed precursor composition, a step of supplying a reactive gas, and a step of purging residual reactive gas are set as a unit cycle, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0154] The unit cycle can be repeated, for example, 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, the desired thin film properties can be effectively exhibited.

[0155] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described herein. In this case, the thin film has excellent step coverage, thickness uniformity, and resistivity, and has excellent density and electrical properties.

[0156] The thin film thus produced preferably has a thickness of 30 nm or less, a resistivity of 5 to 400 μΩ cm based on a thin film thickness of 10 nm, a halogen content of 10,000 ppm or less, and a step coverage rate of 80% or more. Within these ranges, the thin film has excellent performance as a diffusion barrier film and has an effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0157] The thin film can have a thickness of, for example, 1 to 30 nm, preferably 2 to 27 nm, more preferably 3 to 25 nm, and even more preferably 5 to 23 nm, and within this range, there is an effect of excellent thin film properties.

[0158] For example, the thin film may have a resistivity of 5 to 400 μΩ·cm, preferably 5 to 360 μΩ·cm, based on a thin film thickness of 10 nm, and within this range, the thin film has excellent thin film characteristics.

[0159] 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 1000 ppm. Within this range, the thin film has excellent properties and the corrosion of the metal wiring material is reduced. Here, the halogen remaining in the thin film is, for example, Cl2, Cl, or Cl. - The smaller the amount of residual halogen in the thin film, the better the film quality, which is preferable.

[0160] The thin film, for example, has a step coverage rate of 80% or more, preferably 90% or more, more preferably 95% or more. Within this range, even a thin film with a complex structure can be easily deposited on a substrate, which has the advantage of being applicable to next-generation semiconductor devices.

[0161] The manufactured thin film can include one or two types selected from the group consisting of titanium nitride films (TixNy, where 0 < x ≤ 1.2, 0 < y ≤ 1.2, preferably 0.8 ≤ x ≤ 1, 0.8 ≤ y ≤ 1, and more preferably each can be 1), and titanium oxide films (TiO2), and preferably can include a titanium nitride film. In this case, it has the advantage of being useful as a diffusion prevention film, an etching stop film, or a wiring (electrode) for semiconductor elements.

[0162] The thin film can, for example, have a multilayer structure of two or three layers if necessary. The multilayer film with a two-layer structure can, as a specific example, have a structure of a lower layer film - middle layer film, and the multilayer film with a three-layer structure can, as a specific example, have a structure of a lower layer film - middle layer film - upper layer film.

[0163] The lower layer film can be a dielectric film, and for example, can be composed of one or more selected from the group consisting of SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, LaAlO3, BaZrO3, SrZrO3, SrTiO3, BaTiO3, Si3N4, SrO, La2O3, Ta2O5, BaO, TiO2.

[0164] The middle layer film can, for example, contain Ti x N y and preferably can consist of TiN.

[0165] The upper layer film can, for example, be composed of one or more selected from the group consisting of W and Mo.

[0166] Below, preferred embodiments and drawings are presented to aid in understanding the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope of the scope and technical spirit of the present invention. Naturally, such changes and modifications fall within the scope of the appended claims.

[0167] [Example] <Examples 1 to 6 and Comparative Examples 1 to 5> <Reactivity test of auxiliary precursors and thin film precursor compounds> The reactivity of the auxiliary precursors and thin film precursor compounds used in the following Examples 1 to 6 and Comparative Examples 1 to 5 was tested.

[0168] The combinations shown in Table 1 below were selected for the reactivity test.

[0169] As a specific example, H-NMR was measured before mixing the thin film precursor compound and auxiliary precursor shown in Table 1 below, and then H-NMR was also measured after mixing them in a 1:1 molar ratio and storing them in a pressure vessel for 1 hour.

[0170] By comparing the H-NMR spectra before and after mixing, the additional NMR peaks generated were determined to be impurities, and the integral value of the generated NMR peaks was defined as the impurity content.

[0171] When the percentage of the impurity content was less than 0.1%, it was evaluated as no reaction, and when it exceeded 0.1%, it was evaluated as having a reaction. The results are shown in Table 1 below.

[0172] As a specific example, the evaluation method for 1-iodobutane, which was evaluated as no reaction in Table 1 below, is as follows.

[0173] First, as shown in FIG. 1 below, in comparison with the H-NMR measured for 1-iodobutane alone (corresponding to the upper diagram of FIG. 1), 1-iodobutane was mixed with TiCl4 in a 1:1 molar ratio and placed in a pressure vessel for 1 hour, and the H-NMR measured (corresponding to the lower diagram of FIG. 1) showed that the newly generated peak was an impurity, and the content was calculated to be 0.03%, which is less than the standard value of 0.1%, so it was determined that there was no reaction.

[0174] The same evaluation process was repeated for the remaining substances and a response or lack of response was noted.

[0175] [Table 1]

[0176] As shown in Table 1, it was confirmed that, among the 16 combinations presented, 7 combinations in which a co-precursor having an electron-accepting terminal group was mixed with a thin film precursor compound showed reaction stability of less than 0.1%.

[0177] <Examples 1 to 6> The compounds listed in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as a thin film precursor compound. The prepared auxiliary precursor and thin film precursor compound were each placed in a canister and supplied to a vaporizer heated to 150°C at a flow rate of 0.05g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The auxiliary precursor and thin film precursor compound vaporized in the vaporizer were each supplied for 1 second at a 1:1 supply ratio into a deposition chamber loaded with a substrate, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.5Torr.

[0178] Next, 1000 sccm of ammonia was introduced into the reaction chamber as a reactive gas for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated to the temperature shown in Table 2 below. This process was repeated 200 to 400 times to form a TiN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0179] <Comparative Examples 1 to 2> The compounds listed in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as a thin film precursor compound. The prepared auxiliary precursors were placed in canisters and supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The auxiliary precursor vaporized in a vapor state by the vaporizer was introduced into a deposition chamber loaded with a substrate for 1 second, and then argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0180] Next, the prepared TiCl4 was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.05g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The TiCl4 vaporized in the vaporizer was introduced into the deposition chamber for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5Torr.

[0181] Next, 1000 sccm of ammonia was introduced into the reaction chamber as a reactive gas for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated to the temperature shown in Table 2 below. This process was repeated 200 to 400 times to form a TiN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0182] <Comparative Example 3> As auxiliary precursors, the compounds shown in Table 1 above and TiCl4 were prepared as thin film precursor compounds.

[0183] The prepared TiCl4 was placed in a separate canister and supplied to a separate vaporizer heated to 150℃ at a flow rate of 0.05g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The TiCl4 vaporized in the vaporizer was introduced into the deposition chamber for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5Torr.

[0184] Next, the prepared auxiliary precursor was placed in a canister and supplied to a vaporizer heated to 150°C at a flow rate of 0.05g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The auxiliary precursor vaporized in the vaporizer was introduced into a deposition chamber loaded with a substrate for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5Torr.

[0185] Next, 1000 sccm of ammonia was introduced into the reaction chamber as a reactive gas for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated to the temperature shown in Table 2 below. This process was repeated 200 to 400 times to form a TiN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0186] <Comparative Example 4> The compounds shown in Table 1 were prepared as auxiliary precursors, and TiCl4 was prepared as a thin film precursor compound. The prepared auxiliary precursors were placed in canisters and supplied to a vaporizer heated to 150°C at room temperature at a flow rate of 0.05 g / min using a LMFC (Liquid Mass Flow Controller).

[0187] The auxiliary precursor vaporized in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, and then argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging, while the pressure in the reaction chamber was controlled at 2.5 Torr.

[0188] Next, the prepared TiCl4 was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.05g / min using a LMFC (Liquid Mass Flow Controller) at room temperature. The TiCl4 vaporized in the vaporizer was introduced into the deposition chamber for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5Torr.

[0189] Next, 1000 sccm of ammonia was introduced into the reaction chamber as a reactive gas for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated to the temperature shown in Table 2 below. This process was repeated 200 to 400 times to form a TiN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0190] <Comparative Example 5> A TiN thin film was formed by repeating the same process as in Example 1, except that the auxiliary precursor used in Example 1 was replaced with the compound shown in Table 1. [Experimental Example]

[0191] 1) Deposition evaluation (deposition rate per cycle) The deposition rate was evaluated by dividing the thickness of the thin film measured by an ellipsometer, which is a device that can measure optical properties such as the thickness and refractive index of a thin film using the polarization properties of light, by the number of cycles to calculate the thickness of the thin film deposited per cycle, and the results are shown in Table 2 below.

[0192] 2) Thin film resistance evaluation (resistivity) The surface resistance of the thin film thus prepared was measured by a four-point probe method to obtain the surface resistance, and the specific resistance was calculated from the thickness of the thin film.

[0193] The improvement in resistivity (μΩ·cm) was calculated using the following formula 1.

[0194] [Formula 1] Improvement in resistivity (%)=[(resistivity when precursor composition is used−resistivity when auxiliary precursor is not used) / resistivity when auxiliary precursor is not used]×100

[0195] [Table 2]

[0196] * Control group: Measured values ​​for TiN thin film prepared without using auxiliary precursor

[0197] As shown in Table 2, when 1-iodobutane, 2-iodobutane, 2-iodo-2-methylpropane, 2-iodobutane, cyclohexyl iodide, or 1-iodobutane (3-iodo pentane) of the present invention is used as an auxiliary precursor in combination with a thin film precursor compound, In Examples 1 to 6, when the auxiliary precursor was used as a growth inhibitor prior to the addition of the thin film precursor compound (Comparative Examples 1, 2, and 4), when the auxiliary precursor was used as a growth activator after the addition of the thin film precursor compound (Comparative Example 3), or when the auxiliary precursor was replaced with a type that is reactive with the thin film precursor compound (Comparative Example 5), it was shown that the resistivity was reduced to 160 to 358 μΩ·cm while providing the same or similar deposition rate. In particular, it was shown that the resistivity characteristics were significantly reduced by -51% to -10% compared to the control group in which no auxiliary precursor was used, confirming that the thin film growth rate was appropriately controlled and the electrical properties were improved.

[0198] Specifically, in the case of Comparative Example 1, in which 1-iodobutane was used as an auxiliary precursor and a growth inhibitor, the resistivity was 1224 μΩ cm, which was a dramatic increase compared to the control group, which did not use an auxiliary precursor and had a resistivity of 518 μΩ cm.

[0199] In addition, in the case of Comparative Example 2, in which 2-iodobutane was used as the growth inhibitor as an auxiliary precursor, the resistivity was 320 μΩ·cm, which was not significantly different from the control group, which did not use an auxiliary precursor, at 329 μΩ·cm. In the case of Comparative Example 3, in which 2-iodobutane was used as the growth activator, the resistivity was 364 μΩ·cm, which was not significantly different from the control group, which did not use an auxiliary precursor, at 329 μΩ·cm. It was confirmed that there was no effect of improving the electrical properties of the thin film.

[0200] In addition, it was confirmed that the thin film precursor compound did not react with the thin film precursor compound at room temperature, but even in the case of Comparative Example 4 in which an auxiliary precursor not containing the electron-accepting terminal group specific to the present invention was used as a growth inhibitor, it was confirmed that the thin film did not show any improvement in electrical properties.

[0201] Furthermore, it was confirmed that even in the case of Comparative Example 5, in which an auxiliary precursor that reacts with the thin film precursor compound was used in combination with the thin film precursor compound, no improvement effect was observed in the electrical properties of the thin film.

[0202] 3) Impurity reduction properties In order to compare the reduction characteristics of impurities, i.e., process by-products, in the manufactured 10 nm-thick thin film, XPS (X-ray Photoelectron Spectroscopy) analysis was performed for the elements of titanium (Ti), nitrogen (N), Cl (chlorine), carbon (C) and oxygen (O), and the results are shown in Table 3 below.

[0203] [Table 3]

[0204] As shown in Table 3, when the auxiliary precursor according to the present invention was used simultaneously with the thin film precursor compound (Example 6), the Cl and C intensities were both reduced to a level of 0.01%, compared to the case where an inappropriate auxiliary precursor was injected simultaneously with the thin film precursor compound in terms of reactivity with the thin film precursor compound (Comparative Example 5), demonstrating excellent impurity reduction properties. In particular, in the case of Comparative Example 5, an auxiliary precursor that reacts with the thin film precursor compound was injected during the thin film deposition process, so theoretically no carbon should be detected, but it was confirmed that carbon was detected, which is thought to be due to trace amounts of CO and / or CO2 contained in the thin film precursor compound, purge gas, and reaction gas. However, in Example 5 of the present invention, even though an auxiliary precursor that is a hydrocarbon compound was injected during the thin film deposition, it was confirmed that the carbon intensity was reduced compared to Comparative Example 5, which means that the auxiliary precursor according to the present invention has excellent impurity reduction properties.

[0205] In particular, in Comparative Example 5, a compound having a structure similar to that of the auxiliary precursor of the present invention was added at the same time as the precursor composition in the same manner as in the present invention, but the impurity intensity was excessively higher than in Example 6 and even the control group (Ref.), and it was confirmed that there was no effect of improving film quality.

Claims

1. 1. An auxiliary precursor, which is a linear, branched or cyclic alkane compound represented by the following chemical formula 1, and is used in combination with a thin film precursor compound: [Chemical formula 1] AnBmXoYiZj (In the above formula 1, A is carbon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is at least one of bromine (Br) and iodine (I), Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and i and j are 0.)

2. The auxiliary precursor is １ H-NMR spectrum comparison: The auxiliary precursor and the thin film precursor compound were mixed in a 1:1 molar ratio and pressurized, and then the measurement was performed. １ 2. The auxiliary precursor according to claim 1, characterized in that it is a compound exhibiting an integral value of the apex of a newly generated peak in the H-NMR spectrum of less than 0.1%.

3. A linear, branched, or cyclic alkane compound auxiliary precursor represented by the following chemical formula 1: A thin film precursor composition comprising a thin film precursor compound represented by the following chemical formula 2: [Chemical formula 1] AnBmXoYiZj (In the above Chemical Formula 1, A is carbon; B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms; X is at least one of bromine (Br) and iodine (I); Y and Z are independently at least one selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other; n is an integer of 1 to 15; o is an integer of 1 or more; m is 0 to 2n+1; and i and j are 0.) [Chemical formula 2] MxLy (In the above formula 2, x is an integer of 1 to 3; M may be selected from the group consisting of Al, Si, Ca, Ti, Co, Ge, Sr, Zr, Mo, Ru, In, Sn, Ba, Hf, W, Ir, and Pt; y is an integer of 0 to 6; and L is independently H, C, N, O, F, P, S, Cl, Br, or I, or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, F, Cl, and Br.)

4. 2. The thin film precursor composition of claim 1, wherein the auxiliary precursor and the thin film precursor compound have a weight ratio of 1:99 to 99:

1.

5. The thin film precursor composition according to claim 3, wherein the auxiliary precursor is at least one selected from the group consisting of compounds represented by the following Formulas 3 to 14: (In Chemical Formula 3 to Chemical Formula 14, the lines represent bonds, and no separate elements are shown. The points where bonds intersect represent carbon, and hydrogen atoms that satisfy the valence of the carbon are omitted.)

6. 4. The thin film precursor composition of claim 3, wherein the thin film precursor composition is used in an atomic layer deposition (ALD) process, a plasma enhanced atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma enhanced chemical vapor deposition (PECVD) process.

7. 4. A method for forming a thin film, comprising the step of injecting the thin film precursor composition of claim 3 into a chamber and adsorbing the composition on a surface of a substrate that is loaded thereon.

8. i) vaporizing the thin film precursor composition and adsorbing it onto a surface of a substrate loaded inside a chamber; ii) initially purging the interior of the chamber with a purge gas; iii) supplying a reaction gas into the chamber; and iv) a step of secondary purging the inside of the chamber with a purge gas. The thin film forming method according to claim 7 .

9. 8. The method of claim 7, wherein the thin film precursor composition is delivered to an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber by a VFC method, a DLI method, or an LDS method.

10. 8. The method of claim 7, wherein the ratio (mg / cycle) of the auxiliary precursor and the thin film precursor compound contained in the thin film precursor composition fed into the chamber is 1:0.1 to 1:

20.

11. 9. The method of forming a thin film according to claim 8, wherein the reactive gas is a reducing agent, a nitriding agent or an oxidizing agent.

12. 8. The method of claim 7, wherein the deposition temperature is 200 to 700.degree.

13. 8. The method of forming a thin film according to claim 7, wherein the thin film is an oxide film, a nitride film or a metal film.

14. 14. The method of claim 13, wherein the thin film includes a multi-layer structure of two or three layers.

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