Metal thin film precursor composition, and method for forming a thin film using the same

Abstract

The present invention relates to a metal 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 metal thin film precursor composition comprising a metal thin film precursor compound and a growth regulator having a predetermined terminal group and structure. The metal 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, thereby significantly improving step coverage, thin film thickness uniformity, and resistivity even when a thin film is formed on a substrate having a complex structure. Corrosion and deterioration are reduced, and the crystallinity of the thin film is improved, resulting in improved electrical properties of the thin film.

Description

[Technical Field]

[0001] The present invention relates to a metal thin film precursor composition, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom. More specifically, it relates to a metal thin film precursor composition that suppresses side reactions, reduces the concentration of impurities in the thin film, prevents corrosion and degradation of the thin film, improves the electrical properties of the thin film, and appropriately controls the growth rate of the thin film, thereby improving step coverage, thickness uniformity and resistivity of the thin film even when forming a thin film on a substrate with a complex structure. Furthermore, it relates to a metal thin film precursor composition that does not decompose even when mixed with a thin film precursor, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom. [Background technology]

[0002] As the integration density of memory and non-memory semiconductor devices increases day by day, and their structures become increasingly complex, the importance of thin film quality and step coverage is growing ever greater when depositing various thin films onto substrates.

[0003] The aforementioned semiconductor thin films consist of metal nitrides, silicon nitrides, metal oxides, silicon oxides, and metal thin films. Examples of metal nitride thin films or silicon nitride thin films include titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), AlN, TiSiN, TiAlN, TiBN, TiON, TiCN, and SiN. These thin films are generally used as diffusion barriers between the doped silicon layer of a semiconductor and interlayer wiring materials such as aluminum (Al) and copper (Cu). However, when depositing metal thin films such as tungsten (W) and molybdenum (Mo) onto a substrate, they are used as adhesion layers. Various types of metal oxide thin films or silicon nitride thin films have been developed, including SiO2, ZrO2, HfO2, and TiO2. Examples of metal thin films include Ti, Mo, W, and Co. These thin films are typically used for dielectric, insulating, and wiring applications.

[0004] For a thin film deposited on a substrate to achieve excellent uniform physical properties, high step coverage of the formed thin film is essential. Therefore, the ALD (atomic layer deposition) process, which utilizes surface reactions, is used more than the CVD (chemical vapor deposition) process, which mainly utilizes gas-phase reactions. However, problems still remain in achieving 100% step coverage.

[0005] Furthermore, one proposed method to improve step coverage is to reduce the growth rate of the thin film. However, when the deposition temperature is lowered to reduce the growth rate of the thin film, there is a problem in that the amount of residual impurities such as carbon and chlorine in the thin film increases, resulting in a significant decrease in film quality.

[0006] Furthermore, in the case of titanium tetrachloride (TiCl4), which is used to deposit titanium nitride (TiN), a representative of the aforementioned metal nitrides, process by-products such as chlorides remain in the manufactured thin film. This can induce corrosion of metals such as aluminum, leading to the generation of non-volatile by-products and ultimately causing deterioration of the film quality.

[0007] Therefore, there is a need for development of a thin film formation method that enables the formation of thin films with complex structures, has low residual impurities, and does not corrode interlayer wiring materials, as well as development of semiconductor substrates manufactured therefrom. Furthermore, there is a need for development of an auxiliary precursor that can provide uniform thickness and step coverage even with high aspect ratios due to the increasing number of VNAND layers (128, 256, 512, etc.), is difficult to decompose even when used in combination with the thin film precursor, and exhibits outstanding effectiveness. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Korean Published Patent No. 2006-0037241 [Patent Document 2] Korean Published Patent No. 2018-0057059 [Overview of the project] [Problems that the invention aims to solve]

[0009] To solve the problems of the conventional technology described above, the present invention aims to provide an auxiliary precursor that does not decompose even when mixed with a thin film precursor, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom, which not only provides a low band gap, dramatically improves the film quality of the thin film containing the same, suppresses side reactions to appropriately adjust the thin film growth rate, prevents corrosion and degradation by removing process by-products within the thin film, greatly improves the thickness uniformity and resistivity of the step coverage thin film even when forming a thin film on a substrate with a complex structure, but also provides an auxiliary precursor that does not decompose even when used in combination with a thin film precursor.

[0010] Furthermore, the present invention aims to improve the electrical properties of thin films, such as density and resistivity, by improving the crystallinity of the thin film.

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

[0012] To achieve the above objective, the present invention comprises a thin film precursor compound; and a growth regulator. The thin film precursor compound comprises a compound represented by the following chemical formula 1, The present invention provides a metal thin film precursor composition characterized by the growth regulator being a linear, branched, cyclic, or aromatic compound represented by the following chemical formula 2.

[0013] [Chemical formula 1] MxNnLm

[0014] (In the above chemical formula 1, x is an integer from 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, The ligand can be selected from the group consisting of Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, where n is an integer from 0 to 8, and N is a ligand consisting of F, Cl, Br, or I, or two or more combinations selected from the group consisting of F, Cl, Br, and I; m is an integer from 0 to 5, and L is a ligand consisting of H, C, N, O, P, or S, or two or more combinations selected from the group consisting of H, C, N, O, and P.

[0015] [Chemical formula 2] AnBmXoYiZj

[0016] (In the above chemical formula 1, A is carbon, silicon, nitrogen, phosphorus, or sulfur; 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 one or more independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not equal to each other; n is an integer from 1 to 15; o is an integer of 1 or more; m is from 0 to 2n+1; and i and j are integers from 0 to 3.)

[0017] The aforementioned n can be an integer from 1 to 6.

[0018] The aforementioned N may be F, Cl, or Br, or a ligand consisting of two or more types selected from the group consisting of F, Cl, and Br.

[0019] The growth regulator may have a halide-terminal group consisting of Cl, Br, or I, or a combination of two or more selected from the group consisting of Cl, Br, or I.

[0020] The thin film precursor compound may be one or more compounds selected from those represented by the following chemical formulas 3 to 39.

[0021] [Chemical formula 3~Formula 20] JPEG0007836828000001.jpg119127

[0022] [Chemical formula 21~Chemical formula 31] JPEG0007836828000002.jpg78127

[0023] [Chemical formula 32~Chemical formula 39] JPEG0007836828000003.jpg65127

[0024] (In chemical formulas 3 to 39 above, the lines represent bonds, and other elements are not listed. The points where bonds intersect are carbon atoms, and the number of hydrogen atoms required to satisfy the valence of the carbon atoms is omitted. R' and R'' are hydrogen atoms or alkyl groups of carbon atoms 1 through 5, respectively, and R' can be linked to adjacent R' atoms.)

[0025] The growth regulator and the thin film precursor compound may have a weight ratio of 1:99 to 99:1.

[0026] The aforementioned growth regulator may be one or more compounds selected from those represented by the following chemical formulas 40 to 60.

[0027] [Chemical formula 40~Chemical formula 60] JPEG0007836828000004.jpg50127

[0028] (In chemical formulas 40 to 60 above, the lines represent bonds, and other elements are not listed. The points where bonds intersect represent carbon atoms, and the number of hydrogen atoms required to satisfy the valence of the carbon atoms has been omitted.)

[0029] The thin film precursor composition can be used in atomic layer deposition (ALD), plasma atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma chemical vapor deposition (PECVD).

[0030] Furthermore, the present invention provides a thin film formation method characterized by including the step of injecting the aforementioned thin film precursor composition into a chamber and adsorbing it onto the surface of a loaded substrate.

[0031] Furthermore, this invention i) A step in which the growth regulator is vaporized and adsorbed onto the surface of the substrate loaded inside the chamber; ii) A step of primary purging the inside of the chamber with a purge gas; iii) A step of vaporizing the thin film precursor compound inside the chamber and adsorbing it onto a surface different from the portion of the substrate on which the growth regulator is adsorbed, or binding it to the ends of the growth regulator adsorbed on the substrate; iv) The step of secondary purging the inside of the chamber with purge gas; v) The step of supplying the reaction gas inside the chamber; and vi) A step of tertiarily purging the inside of the chamber with a purge gas may be included.

[0032] Furthermore, this invention i-1) A step of vaporizing a metal thin film precursor composition and loading it into a chamber, on the surface of the substrate, adsorbing a thin film precursor compound on a surface different from the portion of the substrate on which the growth regulator is adsorbed, or binding the thin film precursor compound to the ends of the growth regulator adsorbed on the substrate; ii) A step of primary purging the inside of the chamber with a purge gas; v) The step of supplying the reaction gas inside the chamber; and vi-1) The step of further purging the inside of the chamber with a purge gas may be included.

[0033] Furthermore, the present invention i-2) A step in which the thin film precursor compound is vaporized and adsorbed onto the surface of the substrate loaded into the chamber; ii) A step of primary purging the inside of the chamber with a purge gas; iii-1) A step of vaporizing the growth regulator inside the chamber and adsorbing it onto a surface of the substrate different from the adsorbed portion of the growth regulator, or binding it to the ends of the thin film precursor adsorbed on the substrate; iv) The step of secondary purging the inside of the chamber with purge gas; v) The step of supplying the reaction gas inside the chamber; and vi) A step of tertiarily purging the inside of the chamber with a purge gas may be included.

[0034] The metal thin film precursor composition may be transferred into an ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber by VFC, DLI, or LDS.

[0035] The ratio of the amount (mg / cycle) of the growth regulator and the thin film precursor compound in the chamber that constitute the metal thin film precursor composition may be 1:0.1 to 1:20.

[0036] The reaction gas may be a reducing agent, a nitriding agent, or an oxidizing agent.

[0037] The thin film formation method may involve a deposition temperature of 50 to 700°C.

[0038] The thin film may be an oxide film, a nitride film, or a metal film.

[0039] The thin film may have a multilayer structure consisting of two or three layers.

[0040] Furthermore, the present invention provides a semiconductor substrate characterized by being manufactured by the thin-film formation method described above.

[0041] The semiconductor substrate may be a low-resistive metal gate interconnect, a high-aspect-ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA) or 3D NAND. [Effects of the Invention]

[0042] According to the present invention, by adjusting the deposition rate to appropriately adjust the thin film growth rate, an auxiliary precursor is provided that improves step coverage and film quality even when forming a thin film on a substrate having a complex structure.

[0043] Furthermore, because it exhibits reaction stability with respect to thin film precursor compounds, by adjusting the adsorption structure and growth rate of the thin film precursor compounds during thin film formation, process byproducts are reduced, corrosion and degradation are prevented, and the crystallinity of the thin film is improved, thereby providing a growth regulator for thin film formation that improves the resistivity and electrical properties of the thin film. Moreover, it has the effect of providing a thin film formation method using this and a semiconductor substrate manufactured therefrom. [Brief explanation of the drawing]

[0044] [Figure 1] This diagram compares an experiment in which the growth regulator presented in this invention was injected into MoO2Cl2 with a control group experiment in which the growth regulator was not used. [Figure 2]This diagram compares an experiment in which the growth regulator presented in this invention was pre-injected into NbF5 and a control group experiment in which the growth regulator was not used. The left diagram shows the SIMS (secondary ion mass spectrometry) depth profile of the control group NbN thin film, and the right diagram shows the SIMS depth profile of the NbN thin film produced by pre-injecting the growth regulator presented in this invention. [Modes for carrying out the invention]

[0045] The growth regulator, the metal thin film precursor composition, the thin film formation method using the same, and the semiconductor substrate manufactured therefrom will be described in detail below.

[0046] The inventors have confirmed that when a metal thin film precursor compound is adsorbed onto the surface of a substrate loaded inside a chamber, and when a growth regulator having a predetermined end group and structure is adsorbed together with the metal thin film precursor compound, process by-products are reduced by adjusting the adsorption structure and growth rate of the thin film precursor compound, corrosion and degradation are prevented, and the crystallinity of the thin film is improved, resulting in a significant improvement in the resistivity and electrical properties of the thin film. Furthermore, they have confirmed that when a composition containing a metal thin film precursor compound and a specific growth regulator is adsorbed onto the surface of a substrate loaded inside a chamber, when the thin film precursor compound is adsorbed first and then the growth regulator is adsorbed onto the surface of the substrate loaded inside a chamber, or when the growth regulator is adsorbed first and then the thin film precursor compound is adsorbed onto the surface of the substrate loaded inside a chamber, the resistivity is significantly improved in all cases. Based on these findings, the inventors have continued their research and completed the present invention.

[0047] As a preferred embodiment, the thin film formation method may include: i) a step of vaporizing a growth regulator and adsorbing it onto the surface of a substrate loaded into a chamber; ii) a step of primary purging the inside of the chamber with a purge gas; iii) a step of vaporizing a thin film precursor compound into the chamber and adsorbing it onto a surface different from the portion of the substrate where the growth regulator is adsorbed, or binding it to the ends of the growth regulator adsorbed on the substrate; iv) a step of secondary purging the inside of the chamber with a purge gas; v) a step of supplying a reaction gas into the chamber; and vi) a step of tertiary purging the inside of the chamber with a purge gas. In such a case, the thin film growth rate is controlled, and even if the deposition temperature during thin film formation is high, the process by-products generated are effectively removed, which has the advantage of improving the resistivity of the thin film and greatly improving step coverage.

[0048] In another preferred embodiment, the thin film formation method may include i-1) a step of vaporizing a metal thin film precursor composition to adsorb the thin film precursor compound onto a surface of the substrate loaded into the chamber, on a surface different from the portion of the substrate on which the growth regulator is adsorbed, or a step of binding the thin film precursor compound to the ends of the growth regulator adsorbed on the substrate; ii) a step of primary purging the inside of the chamber with a purge gas; v) a step of supplying a reaction gas to the inside of the chamber; and vi-1) a step of additional purging the inside of the chamber with a purge gas. In such a case, the thin film growth rate is controlled, and even if the deposition temperature during thin film formation is high, the process by-products generated are effectively removed, improving the resistivity of the thin film and greatly improving step coverage.

[0049] In another preferred embodiment, the thin film formation method may include i-2) a step of vaporizing a thin film precursor compound and adsorbing it onto the surface of a substrate loaded into a chamber; ii) a step of primary purging the inside of the chamber with a purge gas; iii-1) a step of vaporizing a growth regulator into the inside of the chamber and adsorbing the growth regulator onto a surface of the substrate different from the adsorbed portion, or binding it to the ends of the thin film precursor adsorbed on the substrate; iv) a step of secondary purging the inside of the chamber with a purge gas; v) a step of supplying a reaction gas into the inside of the chamber; and vi) a step of tertiary purging the inside of the chamber with a purge gas. In such a case, the thin film growth rate is controlled, process by-products generated are effectively removed even when the deposition temperature during thin film formation is high, improving the resistivity of the thin film and greatly improving step coverage.

[0050] The metal thin film precursor composition, which includes the growth regulator and the metal thin film precursor compound, can be independently transferred into the chamber, preferably by VFC, DLI, or LDS, and more preferably by LDS.

[0051] The metal thin film precursor composition containing the growth regulator and the metal thin film precursor compound can preferably be used in atomic layer deposition (ALD), plasma atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma chemical vapor deposition (PECVD) processes, and more preferably in atomic layer deposition (ALD) or plasma chemical vapor deposition (PECVD) processes.

[0052] The aforementioned metal thin film precursor compound may include the compound represented by the following chemical formula 1. In this case, the effects targeted by the present invention are well expressed, and there is the advantage that the resistivity of the thin film is improved.

[0053] [Chemical formula 1] M x N n L m

[0054] (In the above chemical formula 1, x is an integer from 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, The ligand can be selected from the group consisting of Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn, where n is an integer from 0 to 8, and N is either F, Cl, Br, or I, or a ligand consisting of two or more combinations selected from the group consisting of F, Cl, Br, and I; m is an integer from 0 to 5, and L is either H, C, N, O, P, or S, or a ligand consisting of two or more combinations selected from the group consisting of H, C, N, O, and P.

[0055] As an example, the metal thin film precursor compound is one in which, in the chemical formula 1, x is an integer from 1 to 2, 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, The ligand can be selected from the group consisting of Tl, Pb, Bi, Pt, At, and Tn, where n is an integer from 1 to 8, and N is either F, Cl, Br, or I, or a ligand consisting of two or more combinations selected from the group consisting of F, Cl, Br, and I; m is an integer from 0 to 5, and L is either H, C, N, O, P, or S, or a ligand consisting of two or more combinations selected from the group consisting of H, C, N, O, and P. In this case, the effect intended by the present invention is well expressed, and there is the advantage of exhibiting improved resistivity.

[0056] The aforementioned n can preferably be an integer from 1 to 7, and more preferably an integer from 1 to 6, and within this range, there is the advantage of a reduction in process by-products and superior adsorption to the substrate. Furthermore, N can be a halogen element, preferably fluorine, chlorine, or bromine, and more preferably fluorine or chlorine, and within this range, there is the advantage of a reduction in process by-products and superior adsorption to the substrate. Furthermore, as an example, N can be chlorine, in which case the crystallinity of the thin film is improved, and there is the advantage of suppressing side reactions and having a superior effect in reducing process by-products.

[0057] In the aforementioned chemical formula 1, N may, as another preferred example, be iodine or bromine, which has the advantage of being more suitable for processes requiring low-temperature deposition.

[0058] The metal thin film precursor compound may be a branched or cyclic compound represented by the chemical formula 1, in which 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 one or more selected independently from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other, n is an integer from 1 to 15, o is an integer of 1 or more, m is from 0 to 2n+1, and i and j are 0. In this case, the effects intended by the present invention are well expressed, exhibiting improved resistivity, improved crystallinity of the thin film, suppression of side reactions, and a superior reduction in process by-products.

[0059] The aforementioned metal thin film precursor compound may be a halogen-containing compound, and specific examples include the compounds represented by chemical formulas 3 to 39 below. Here, the compounds represented by chemical formulas 3 to 39 can be selected independently of each other or used in combination.

[0060] [Chemical formula 3~Chemical formula 20] JPEG0007836828000005.jpg119127

[0061] [Chemical formula 21~Chemical formula 31] JPEG0007836828000006.jpg78127

[0062] [Chemical formula 32~Chemical formula 39] JPEG0007836828000007.jpg65127

[0063] (In chemical formulas 3 to 39 above, the lines represent bonds, and other elements are not listed. The points where bonds intersect are carbon atoms, and the number of hydrogen atoms required to satisfy the valence of the carbon atoms is omitted. R' and R'' are hydrogen atoms or alkyl groups of carbon atoms 1 to 5, respectively, and R' may be linked to an adjacent R' atom.)

[0064] Furthermore, the metal thin film precursor composition of the present invention comprises a thin film precursor compound and a growth regulator. The thin film precursor compound includes the compound represented by the chemical formula 1 described above, The growth regulator is characterized by being a linear, branched, cyclic, or aromatic compound represented by the following chemical formula 2. In this case, the desired effect is well expressed, and there is the advantage of improving the resistivity of the thin film.

[0065] [Chemical formula 2] AnBmXoYiZj

[0066] (In the above chemical formula 1, A is carbon, silicon, nitrogen, phosphorus, or sulfur; 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 one or more independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other; n is an integer from 1 to 15; o is an integer of 1 or more; m is from 0 to 2n+1; and i and j are integers from 0 to 3.)

[0067] The growth regulator and the thin 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.

[0068] The growth regulator may be a branched or cyclic compound represented by the chemical formula 1, in one example, where 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 one or more selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other, n is an integer from 1 to 15, o is an integer of 1 or more, m is from 0 to 2n+1, and i and j are 0. In this case, the effect intended by the present invention is well expressed, and there is an advantage in that it exhibits improved resistivity.

[0069] The aforementioned X is a halogen element, preferably fluorine, chlorine, bromine, or iodine, and more preferably chlorine or bromine. Within this range, there is the advantage of a reduction in process by-products and superior adsorption to the substrate. Furthermore, as an example, X may be chlorine, which has the advantage of improving the crystallinity of the thin film, suppressing side reactions, and having a superior effect in reducing process by-products.

[0070] In the aforementioned chemical formula 1, X may be iodine or bromine, as another preferred example, which has the advantage of being more suitable for processes requiring low-temperature deposition.

[0071] The growth regulator may be a branched or cyclic compound represented by the chemical formula 1, in which 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 one or more selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other, n is an integer from 1 to 15, o is an integer of 1 or more, m is from 0 to 2n+1, and i and j are 0. In this case, the effects intended by the present invention are well expressed, and there is an advantage in that improved resistivity is exhibited.

[0072] The growth regulator may be a branched or cyclic compound represented by the chemical formula 1, in which 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 one or more independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not the same as each other, n is an integer from 1 to 15, o is an integer of 1 or more, m is from 0 to 2n+1, and i and j are 0. In this case, the effects targeted by the present invention are well expressed, exhibiting improved resistivity, improved crystallinity of the thin film, suppression of side reactions, and a superior reduction in process by-products.

[0073] The growth regulator may, in a preferred embodiment, include a hydrocarbon compound containing an electron-accepting end group. The hydrocarbon compound may be a substance that does not react with the thin film precursor compound. By adjusting the adsorption structure and growth rate of the thin film precursor compound when using the growth regulator, process byproducts are reduced. This allows for adjustment of the deposition rate to appropriately lower the thin film growth rate, improving step coverage and film quality even when forming a thin film on a substrate with a complex structure. This prevents corrosion and degradation, improves the crystallinity of the thin film, and thereby improves the resistivity and electrical properties of the thin film.

[0074] The hydrocarbon compound may preferably be a compound having a structure in which one or more selected from the group consisting of alkanes and cycloalkanes are substituted with electron-accepting end groups. In this case, there are advantages such as low reactivity and solubility, easy moisture control, and improved step coverage in high-aspect-ratio trench structures during thin film formation.

[0075] As a more preferred example, the hydrocarbon compound is C1-C 10 Alkanes, or C3~C 10 It may contain cycloalkanes, preferably C3-C3. 10 This is a cycloalkane, which has the advantage of low reactivity and solubility, making moisture management easy.

[0076] In this document, C1, C3, etc., refer to the number of carbon atoms.

[0077] The cycloalkane is preferably C3-C 10 The material may be a monocycloalkane, and among these monocycloalkanes, cyclopentane is preferred in the vapor deposition process because it is a liquid at room temperature and has the highest vapor pressure, but the material is not limited to this.

[0078] In this invention, unless otherwise specified, the term "electron-accepting end group" refers to a functional group that can provide improved film quality when bonded to a thin film precursor compound.

[0079] The electron-accepting terminal group may, for example, be an ortho-directed or para-directed deactivation group.

[0080] The aforementioned terms, "ortho-directed and para-directed deactivation groups," refer to deactivation groups that exhibit directionality to the ortho and para positions when using precursor compounds having a benzene ring, unless otherwise specified.

[0081] The electron-accepting terminal group may, as an example, be an electron acceptor having an electronegativity of 2.0 to 4.0, preferably 2.0 to 3.0.

[0082] Unless otherwise specified, the electronegativity range may be satisfied by the active group when using a precursor compound that does not have a benzene ring.

[0083] The electron-accepting end group is, in specific examples, a halogen element, preferably fluorine, chlorine, bromine, or iodine, and more preferably bromine or iodine. Within this range, there is an advantage in that the reduction of process by-products and the improvement of step coverage are better. In addition, X can be iodine as an example, in which case there is an advantage in that it is more suitable for processes that require low-temperature deposition. In particular, X can be iodine alone, in which case it is even more effective in improving the film quality of the thin film because it does not excessively increase the impurity content.

[0084] The growth regulator may, in a more preferred embodiment, contain a halide-terminated group consisting of Cl, Br, or I, or a combination of two or more selected from the group consisting of Cl, Br, or I. In this case, the effects targeted by the present invention are well expressed, resulting in improved resistivity, improved crystallinity of the thin film, suppression of side reactions, and a superior reduction in process by-products.

[0085] In a more preferred embodiment, the growth regulator has a tert-carbocation skeleton, which can prevent the residue of impurities after thin film production, and has the advantage of being particularly effective in preventing carbon from remaining.

[0086] The reactivity between the hydrocarbon compound and the thin-film precursor compound is determined by comparing the H-NMR spectrum measured before mixing the hydrocarbon compound and the thin-film precursor compound with the H-NMR spectrum measured after pressurizing a 1:1 molar mixture for 1 hour. When the peak integral value of the resulting NMR peak is taken as the impurity content, the impurity content (%) is less than 0.1%. By adjusting the adsorption structure and growth rate of the thin-film precursor compound when using a growth regulator, process byproducts are reduced, and the deposition rate can be adjusted to appropriately lower the thin-film growth rate. This improves step coverage and film quality even when forming thin films on substrates with complex structures, thereby preventing corrosion and degradation, improving the crystallinity of the thin film, and thus improving the resistivity and electrical properties of the thin film.

[0087] Due to the aforementioned reactivity, the growth regulator has the advantage of easily adjusting the viscosity and vapor pressure of the thin film precursor compound without interfering with the behavior of the thin film precursor compound.

[0088] While exhibiting the reactivity described above, the hydrocarbon compounds containing the electron-accepting end groups may, for example, be halogen-substituted linear or branched alkane compounds or cycloalkane compounds.

[0089] Specific examples include tert-butyl iodide (2-Iodo-2-methyl propane), 1-iodobutane, 2-iodobutane, 2-iodo-3-methylbutane, 3-iodo-2,4-dimethylpentane, cyclohexyl iodide (iodo-cyclohexane), cyclopentyl iodide (iodo-cyclopentane), and tert-butyl bromide (2-Iodo-2-methyl propane). 2-bromo-2-methylpropane), 1-bromobutane, 2-bromobutane, 2-bromo-3-methylbutane, 3-bromo-2,4-dimethylpentane, cyclohexyl bromide, cyclopentyl bromide, tert-butyl chloride, 1-chlorobutane, 2-chlorobutane, 2-chloro-3-methylbutane, 3-chloro-2,4-dimethylpentane, cyclohexyl chloride, and cyclopentyl chloride It is one or more selected from the group consisting of tert-butyl iodide, tert-butyl bromide, tert-butyl chloride, 1-iodobutane, 2-iodobutane, 1-bromobutane, 2-bromobutane, 1-chlorobutane, and 2-chlorobutane. In this case, it has the advantage of effectively protecting the substrate surface as a growth regulator while adjusting the adsorption structure and growth rate of the thin film precursor compound, and effectively removing process by-products.

[0090] As mentioned above, the hydrocarbon compounds may be halogen-substituted hydrocarbons, and specific examples include the compounds represented by chemical formulas 40 to 60 below. Here, the compounds represented by chemical formulas 40 to 60 can be selected independently of each other or used in combination.

[0091] [Chemical formula 40~Chemical formula 60] JPEG0007836828000008.jpg50127

[0092] (In Chemical Formulas 40 to 60, the lines represent bonds. At the points where bonds intersect without specifying other elements, the atom is carbon, and the hydrogen atoms satisfying the valence of carbon are omitted.)

[0093] The metal thin film precursor composition, metal thin film precursor compound, and growth regulator are preferably used in an atomic layer deposition (ALD) process, plasma atomic layer deposition (PEALD) process, chemical vapor deposition (CVD) process, or plasma enhanced chemical vapor deposition (PECVD) process. In this case, there is an advantage that the surface of the substrate can be effectively protected as a growth regulator without inhibiting the adsorption of the thin film precursor compound, and the process by-products can be effectively removed.

[0094] The growth regulator is preferably a liquid at normal temperature (22°C), with a density of 0.8 to 2.5 g / cm 3 or 0.8 to 1.7 g / cm 3 and a vapor pressure (20°C) of 0.1 to 300 mmHg or 1 to 300 mmHg, and a solubility in water (25°C) that can be 200 mg / L or less. Within this range, there is an effect of excellent step coverage, film thickness uniformity, and film quality improvement.

[0095] More preferably, the growth regulator has a density of 0.75 to 2.0 g / cm 3 or 0.8 to 1.7 g / cm 3 and a vapor pressure (20°C) of 0.1 to 1000 mmHg, and a solubility in water (25°C) that can be 2000 mg / L or less. Within this range, there is an excellent effect on step coverage, film thickness uniformity, and film quality improvement.

[0096] Furthermore, the thin film formation method of the present invention is characterized in that, as another preferred example, it includes the step of injecting the metal thin film precursor composition into an ALD chamber and adsorbing it onto the loaded substrate surface. In this case, there are advantages such as an appropriate increase in the thin film growth rate, effective removal of process by-products generated during thin film formation, a reduction in impurities in the thin film, and a significant improvement in crystallinity.

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

[0098] The aforementioned thin film formation method, for example, has an evaporation temperature of 50 to 700°C, preferably 250 to 500°C, and specific examples include 250 to 450°C, 280 to 450°C, or 350 to 420°C. Within this range, there is an advantage in that the thin film resistivity, step coverage, and other properties are greatly improved.

[0099] In the above chemical formula 1, M is titanium, tungsten, molybdenum, silicon, hafnium, zirconium, indium, germanium, or niobium, preferably titanium, tungsten, molybdenum, or niobium.

[0100] In the above chemical formula 1, N is a halogen element, preferably fluorine, chlorine, bromine, or iodine, and more preferably fluorine, chlorine, or bromine. Within this range, there is an advantage of further reduction of process by-products and superior adsorption to the substrate. Furthermore, N may be fluorine or chlorine as an example, in which case the crystallinity of the thin film is improved, side reactions are suppressed, and the effect of reducing process by-products is further superior.

[0101] In the aforementioned chemical formula 1, L may be H, C, N, O, P, or S, or a ligand consisting of two or more elements selected from the group consisting of H, C, N, O, and P. In this case, the crystallinity of the thin film is improved, side reactions are suppressed, and the reduction of process by-products is further enhanced.

[0102] The compound represented by chemical formula 1 is a compound having a halogenating group in the central metal, and a specific example is one or more selected from the group consisting of molybdenum(V) chloride (MoCl5), molybdenum oxytetrachloride (MoOCl4), molybdenum dichloride deoxide (MoO2Cl2), molybdenum(VI) fluoride (MoF6), tungsten(VI) chloride (WCl6), tungsten(VI) fluoride (WF6), niobium(V) chloride (NbCl5), or niobium(V) fluoride (NbF6). In this case, the effect of removing process by-products is significant, and the step coverage and adsorption effect to the substrate are excellent.

[0103] The compound represented by the above chemical formula 1 is a halogen-substituted tert-alkyl compound, and specific examples include tetrachlorotitanium, 2-chloro-3-methyltitanium, 2-chloro-2-methyltitanium, tetrabromotitanium, 3-bromo-3-methyltitanium, 3-bromo-3-methyltitanium, tetrachlorotitanium, 2-chloro-3-methyltungsten, 2-chloro-2-methyltungsten, tetrabromotungsten, 3-bromo-3-methyltungsten, 3-bromo-3-methyltungsten, tetrachloromolybdenum (molybdenum), 2-chloro-3-methylmolybdenum, 2-chloro-2-methylmolybdenum, tetrabromolybdenum, 3-bromo-3-methylmolybdenum, 3-bromo-3-methylmolybdenum, tetrachloroha One or more selected from the group consisting of phnium, 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, or 3-bromo-3-methylindium, in which case the effect of removing process by-products is significant, and the effect of improving step coverage and adsorption to the substrate is excellent.

[0104] The compound represented by chemical formula 1 (or conductive compound) is described with specific examples, but is not limited thereto; it is not particularly limited as long as it is a thin-film precursor compound commonly used in ALD (atomic layer deposition).

[0105] In the present invention, unless otherwise specified, the term "conductive compound" refers to a substance having electron donors or acceptors that possesses conductivity and whose properties can be influenced by their structure and the oxidation state of charge transfer.

[0106] Specific examples include one or more selected from the group consisting of metal thin film precursor compounds, metal oxide film precursor compounds, metal nitride film precursor compounds, and silicon nitride film precursor compounds. The metal may preferably include one or more 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, niobium, and iridium.

[0107] The metal film precursor, metal oxide film precursor, and metal nitride film precursor may each be one or more selected from the group consisting of, for example, 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.

[0108] The metal oxide film precursor may be independently selected from the group consisting of PtO, PtO2, RuO2, IrO2, SrRuO3, BaRuO3, and CaRuO3, as an example.

[0109] As specific examples, the metal film precursor, metal oxide film precursor, and metal nitride film precursor are, respectively, tetrachlorotitanium, tetrachlorogermanium, tetrachlorotin, tris(isopropyl)ethylmethylaminogermanium, tetraethoxyl germanium, tetramethyltin, tetraethyltin, bisacetylacetonatetin, trimethylaluminum, tetrakis(dimethylamino)germanium, bis(n-butylamino)germanium, tetrakis(ethylmethylamino)tin, tetrakis(dimethylamino)tin, and Co2(CO)8(dicobalt). It may be one or more selected from the group consisting of octacarbonyl, Cp2Co (biscyclopentadienyl cobalt), Co(CO)3(NO) (cobalt tricarbonyl nitrosyl), and CpCo(CO)2 (cobalt dicarbonyl cyclopentadienyl), but is not limited to these.

[0110] Examples of the silicon nitride film precursors 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(NHi 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 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, (Nn 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, (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, (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 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( nPrNCH2CH2N n 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(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 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 It may be one or more selected from the group consisting of Bu)2, but is not limited to this.

[0111] The aforementioned n Pr stands for n-propyl, i Pr stands for isopropyl, n Bu is n-butyl, i Bu is iso-butyl, t Bu stands for tert-butyl.

[0112] The thin film precursor compound is, as a preferred example, 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, PtO 2It may contain one or more selected from the group consisting of RuO2, IrO2, SrRuO3, BaRuO3, and CaRuO3, in which case the effects to be achieved in this invention can be fully obtained.

[0113] The titanium tetrahalide may be used as a metal precursor in a thin-film forming composition. The titanium tetrahalide may be at least one selected from the group consisting of TiF4, TiCl4, TiBr4, and TiI4, for example, TiCl4 is preferred from an economic standpoint, but is not limited thereto.

[0114] For example, titanium tetrahalide exhibits excellent thermal stability and does not decompose at room temperature, remaining in a liquid state. Therefore, it can be usefully used as a precursor in ALD (atomic layer deposition) to deposit thin films.

[0115] The thin-film precursor compound can, for example, be mixed with a non-polar solvent (excluding those that overlap with the hydrocarbon compound) and introduced into the chamber. In this case, there is the advantage that the viscosity and vapor pressure of the thin-film precursor compound can be easily adjusted.

[0116] The nonpolar solvent may preferably be one or more selected from the group consisting of alkanes and cycloalkanes. In this case, there is an advantage that the step coverage improves even when the deposition temperature during thin film formation increases, while containing an organic solvent with low reactivity and solubility, and easy moisture control.

[0117] As a more preferred example, the nonpolar solvent is C1-C 10 Alkanes, or C3~C 10 It may contain cycloalkanes, preferably C3-C3. 10 This is a cycloalkane, which has the advantage of low reactivity and solubility, making moisture management easy.

[0118] In this document, C1, C3, etc., refer to the number of carbon atoms.

[0119] The cycloalkane is preferably C3-C 10 These can be monocycloalkanes, and among these monocycloalkanes, cyclopentane is liquid at room temperature, has the highest vapor pressure, and is preferred in the vapor deposition process, but is not limited to this.

[0120] The aforementioned nonpolar solvent, for example, has a solubility in water (at 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, it has the advantage of low reactivity with the thin-film precursor compound and easy moisture control.

[0121] In this description, solubility is not particularly limited, as long as it is based on measurement methods and standards commonly used in the art to which this invention pertains. For example, a saturated solution can be measured by HPLC.

[0122] The nonpolar solvent may preferably be present in an amount of 5 to 95% by weight relative to the total weight of the thin film precursor compound and the nonpolar solvent combined, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and even more preferably 70 to 90% by weight.

[0123] If the amount of the nonpolar solvent added exceeds the upper limit, it induces impurities, leading to an increase in both resistance and the amount of impurities in the thin film. Conversely, if the amount of the organic solvent added is below the lower limit, it has the disadvantage of having less effect on improving step coverage due to solvent addition and reducing impurities such as chloride (Cl) ions.

[0124] Preferably, the compound represented by chemical formula 1 or the conductive compound is a liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm³. 3 Or 0.8~1.5 g / cm³ 3Therefore, the vapor pressure (at 20°C) can be between 0.1 and 300 mmHg or between 1 and 300 mmHg, and within this range, it has the effect of providing excellent step coverage, uniformity of thin film thickness, and improvement of film quality.

[0125] More preferably, the compound represented by chemical formula 1 or the conductive compound has a density of 0.7 to 2.0 g / cm³. 3 Or 0.8-1.8 g / cm³ 3 Therefore, the vapor pressure (at 20°C) can range from 0.1 to 1000 mmHg, and within this range, it exhibits excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0126] The ratio of the growth regulator to the amount (mg / cycle) of the thin film precursor compound introduced into the chamber 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 effect of improving step coverage and reducing process by-products is significant.

[0127] The precursor composition comprising the growth regulator and the thin film precursor compound is preferably used in atomic layer deposition (ALD), plasma atomic layer deposition (PEALD), chemical vapor deposition (CVD), or plasma chemical vapor deposition (PECVD) processes. In this case, it has the advantages of significantly reducing process by-products, excellent step coverage, improved thin film density, and excellent electrical properties of the thin film.

[0128] The present invention provides a thin film formation method that includes the step of injecting the precursor composition into a chamber and adsorbing it onto the loaded substrate surface. In this case, side reactions during thin film formation can be suppressed, the thin film growth rate can be adjusted, process by-products in the thin film are reduced, corrosion and degradation are reduced, the crystallinity of the thin film is improved, and even when forming a thin film on a substrate with a complex structure, the step coverage and electrical properties of the thin film are greatly improved.

[0129] In the step of adsorbing the precursor composition onto the substrate surface, the feeding time for supplying the thin film precursor composition, the metal thin film precursor compound constituting the thin film precursor composition, or the growth regulator to the substrate surface 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 per cycle. Within this range, the thin film growth rate is low, and there are advantages in terms of step coverage and economic efficiency.

[0130] In this description, the feeding time of the precursor composition is based on a chamber volume of 15-20 L and a flow rate of 0.5-100 mg / s, and more specifically, on a chamber volume of 18 L and a flow rate of 1-25 mg / s.

[0131] The thin film formation method may, in a preferred embodiment, include: i) vaporizing the precursor composition and adsorbing it onto the surface of a substrate loaded into a chamber; ii) primary purging the inside of the chamber with a purge gas; iii) supplying a reaction gas to the inside of the chamber; and iv) secondary purging the inside of the chamber with a purge gas. In this case, steps i) to iv) are considered as a unit cycle, and the cycle can be repeated until a thin film of the desired thickness is obtained. When the growth regulator of the present invention is introduced together with the thin film precursor compound and adsorbed onto the substrate within one cycle, even when deposition is performed at a low temperature, the process by-products generated are effectively removed, the resistivity of the thin film is improved, and the step coverage is greatly enhanced.

[0132] In the thin film formation method of the present invention, as a preferred example, the growth regulator of the present invention can be added together with the thin film precursor compound within one cycle and adsorbed onto the substrate. In this case, even if the thin film is deposited at a low temperature, the thin film growth rate can be appropriately reduced, thereby significantly reducing process by-products and greatly improving step coverage. This can increase the crystallinity of the thin film and improve its resistivity. Furthermore, even when applied to semiconductor devices with a large aspect ratio, the thickness uniformity of the thin film is greatly improved, which has the advantage of ensuring the reliability of the semiconductor device.

[0133] In the aforementioned thin film formation method, for example, when the growth regulator is adsorbed simultaneously with the deposition of the thin film precursor compound, the unit cycle can be repeated 1 to 99,999 times as needed, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film thickness can be obtained, and the property improvement effects, including resistivity, that the present invention aims to achieve can be fully obtained.

[0134] Furthermore, as shown in the examples described later, if the growth regulator is adsorbed before or after the deposition of the thin film precursor compound, the improvement in physical properties, including resistivity, that is obtained when the growth regulator and the thin film precursor compound are added and deposited simultaneously can also be obtained.

[0135] When the growth regulator and the thin film precursor compound are adsorbed together or sequentially onto a substrate, the amount of purge gas introduced into the chamber during the purging stage of the unadsorbed precursor composition is not particularly limited as long as it is sufficient to remove the unadsorbed precursor composition. For example, it 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 is sufficiently removed, resulting in the uniform formation of the thin film and preventing deterioration of the film quality. Here, the amounts of purge gas and precursor composition introduced are based on one cycle, and the volume of the precursor composition refers to the volume of vaporized metal thin film precursor composition.

[0136] As a specific example, if the precursor composition is injected at a flow rate of 1.66 mL / s and an injection time of 0.5 sec (per cycle), and a purge gas is injected at a flow rate of 166.6 mL / s and an injection time of 3 sec (per cycle) to purge the unadsorbed precursor composition, the amount of purge gas injected is 602 times the amount of metal thin film precursor composition injected.

[0137] Furthermore, the amount of purge gas introduced into the chamber during the purging stage, which is performed immediately after the reaction gas supply stage, can be, for example, 10 to 10,000 times the volume of reaction gas introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and the desired effect can be sufficiently obtained within this range. Here, the amounts of purge gas and reaction gas introduced are based on one cycle each.

[0138] The aforementioned metal thin film precursor composition and thin film precursor compound may be transferred into an ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber, preferably by VFC, DLI, or LDS, and more preferably by LDS into an ALD chamber.

[0139] The ratio of the amount (mg / cycle) of the growth regulator and the thin-film precursor compound constituting the precursor composition to be introduced into the chamber 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 effect of improving step coverage and reducing process by-products is greatest.

[0140] As an example, when using the precursor composition, the thin film formation method described above yields an improvement in resistivity (μΩ·cm) of -50% or less, calculated by the following formula 1, preferably between -50% and -10%, within which step coverage, resistivity characteristics, and film thickness uniformity are excellent.

[0141] [Formula 1] Resistivity Improvement (%) = [(Resistivity with growth regulator - Resistivity without growth regulator) / Resistivity without growth regulator] x 100

[0142] In the above formula 1, the degree of improvement in resistivity when a growth regulator is used and when it is not used refers to the respective conductivity characteristics, i.e., resistivity (μΩ·cm). This resistivity can be determined, for example, by measuring the surface resistance using the four-point probe method and then obtaining the value of the thin film thickness.

[0143] In the above formula 1, "when a growth regulator is used" means the case in which a thin film is manufactured by adsorbing both a growth regulator and a thin film precursor compound onto a substrate during the thin film deposition process, and "when a growth regulator is not used" means the case in which a thin film is manufactured by adsorbing a thin film precursor compound onto a substrate without using a growth regulator during the thin film deposition process.

[0144] The aforementioned thin film formation method allows the residual halogen intensity (c / s) within the thin film, measured based on XPS and based on a thin film thickness of 100 Å (10 nm), to be preferably 100,000 or less, more preferably 90,000 or less, even more preferably 80,000 or less, and even more preferably 76,000 or less. Within this range, the effect of preventing corrosion and degradation is excellent.

[0145] The aforementioned thin film formation method allows the residual halogen intensity (c / s) in a 100 Å (10 nm) thin film, measured based on SIMS (Secondary Ion Mass Spectrometry), to be preferably 100,000 or less, more preferably 90,000 or less, even more preferably 80,000 or less, and even more preferably 76,000 or less. Within this range, the effect of preventing corrosion and degradation is excellent.

[0146] In this description, the purging is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, resulting in deposition of a single atomic layer (atomic mono-layer) or something close to it, which has the advantage of being advantageous in terms of film quality.

[0147] The aforementioned ALD (atomic layer deposition) or PEALD (plasma atomic layer deposition) processes are extremely advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios. In particular, their self-limiting thin film growth mechanism offers advantages such as excellent conformality, uniformity, and precise thickness control.

[0148] The aforementioned thin film formation method can be carried out, for example, at a deposition temperature in the range of 50 to 700°C, preferably in the range of 300 to 700°C, more preferably in the range of 400 to 650°C, and even more preferably in the range of 400 to 600°C. Within this range, there is an effect of growing a thin film with excellent film quality while embodying the characteristics of the ALD process.

[0149] The aforementioned thin film formation method can be carried out, for example, with 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, and has the effect of obtaining a thin film of uniform thickness within this range.

[0150] In this description, the deposition temperature and deposition pressure may be measured by the temperature and pressure formed within the deposition chamber, or by the temperature and pressure applied to the substrate within the deposition chamber.

[0151] The thin film formation method may preferably include the steps of raising the temperature inside the chamber to the deposition temperature before introducing the thin film precursor composition, or the growth regulator or metal thin film precursor compound constituting the thin film precursor composition, into the chamber; and / or purging the chamber by injecting an inert gas into the chamber before introducing the precursor composition into the chamber.

[0152] Furthermore, the present invention may include a thin film manufacturing apparatus capable of embodying the thin film manufacturing method, comprising: an ALD chamber; a first vaporizer for vaporizing a growth regulator; a first transfer means for transferring the vaporized growth regulator into the ALD chamber; a second vaporizer for vaporizing a thin film precursor compound; and a second transfer means for transferring the vaporized thin film precursor compound into the ALD chamber.

[0153] Furthermore, the present invention may include a mixing means in the thin film manufacturing apparatus for mixing the vaporized growth regulator and the vaporized thin film precursor compound, and the precursor composition may be mixed in advance before being transferred into the chamber.

[0154] Here, the chamber, vaporizer, transfer means, or mixing means is not particularly limited, as long as it is a chamber, vaporizer, transfer means, or mixing means commonly used in the art to which the present invention belongs.

[0155] As a specific example, the thin film formation method using the ALD process described above is first positioned inside a deposition chamber capable of atomic layer deposition on which a thin film will be formed on top.

[0156] The substrate may include semiconductor substrates such as silicon substrates and silicon oxide.

[0157] The substrate may have a conductive layer or an insulating layer further formed on its upper surface.

[0158] To deposit a thin film onto a substrate located inside the deposition chamber, the growth regulator described above and a thin film precursor compound or a mixture thereof with a nonpolar solvent are prepared.

[0159] Subsequently, each component is injected into a vaporizer, converted into a vapor, and sequentially transferred to the deposition chamber for adsorption onto the substrate. Alternatively, the thin-film forming composition can be manufactured in advance, converted into a vapor using a single vaporizer, transferred to the deposition chamber, and adsorbed onto the substrate. The unadsorbed precursor composition (thin-film forming composition) is then removed by purging.

[0160] According to one embodiment of the present invention, since a growth regulator that does not react with the metal thin film precursor compound is used, the growth regulator can be largely removed during purging.

[0161] In this description, the method for transferring growth regulators and metal thin film precursor compounds (compositions for thin film formation) to the deposition chamber can, for example, be a method that utilizes a gaseous flow controller (MFC) to transfer volatile gases (VFC), or a method that utilizes a liquid mass flow controller (LMFC) to transfer liquids (Liquid Delivery System (LDS)), with the LDS method being preferred.

[0162] In this process, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) may be used as the transport gas or diluent gas for moving the growth regulator and metal thin film precursor compound onto the substrate, but are not limited to these.

[0163] In this description, an inert gas may be used as the purge gas, and preferably the transport gas or diluent gas mentioned above can be used.

[0164] 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 art to which the present invention belongs, and preferably includes a reducing agent, a nitride 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, where a metal nitride thin film is formed if a nitride agent is used, and a metal oxide thin film is formed if an oxidizing agent is used.

[0165] 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.

[0166] Next, an inert gas is used to purge any unreacted residual reaction gas. This removes not only excess reaction gas but also any by-products that have been generated.

[0167] As described above, the thin film formation method, as an example, can be performed by repeating a unit cycle consisting of the steps of adsorbing a precursor composition onto a substrate, purging unadsorbed precursor composition, supplying a reaction gas, and purging residual reaction gas, in order to form a thin film of a desired thickness.

[0168] As another example, the thin film formation method may consist of a unit cycle comprising the steps of adsorbing a metal thin film precursor compound onto a substrate, purging unadsorbed metal thin film precursor compounds, adsorbing a growth regulator onto the substrate, purging unadsorbed or physically adsorbed growth regulators, supplying a reaction gas, and purging residual reaction gases. This unit cycle can be repeated to form a thin film of a desired thickness.

[0169] As another example, the thin film formation method can be described as having a unit cycle consisting of the steps of adsorbing a growth regulator onto a substrate, purging unadsorbed growth regulator, adsorbing a metal thin film precursor compound onto a substrate, purging unadsorbed metal thin film precursor compound and, consequently, physically adsorbed growth regulator, supplying a reaction gas, and purging residual reaction gas, and repeating this unit cycle to form a thin film of a desired thickness.

[0170] The aforementioned 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, and within this range, the desired thin film characteristics are effectively achieved.

[0171] 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 step coverage of the thin film, the uniformity of the thin film thickness, and the resistivity characteristics are greatly improved, and the density and electrical properties of the thin film are also excellent.

[0172] The manufactured thin film preferably has a thickness of 30 nm or less, a resistivity of 5 to 2000 μΩ·cm based on a thin film thickness of 10 nm, a halogen content of 10,000 ppm or less, and a step coverage ratio of 80% or more. Within this range, it exhibits excellent performance as a diffusion-blocking film, dielectric film, or insulating film, and has the effect of reducing corrosion of metal wiring materials, but is not limited to this.

[0173] The thin film may 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, it exhibits excellent thin film properties.

[0174] As an example, the aforementioned thin film may have a reference resistivity of 5 to 2000 μΩ·cm, preferably 5 to 1900 μΩ·cm, based on a thin film thickness of 10 nm, and exhibits excellent thin film properties within this range.

[0175] The aforementioned thin film has a halogen content, as analyzed by XPS (X-ray Photoelectron Spectroscopy), preferably 10,000 ppm or less, or 0.001 to 8,000 ppm, more preferably 0.001 to 5,000 ppm, and even more preferably 0.001 to 1,000 ppm. Within this range, it exhibits excellent thin-film properties while reducing corrosion of the metal wiring material. Here, the halogen remaining in the thin film is, for example, Cl2, Cl, or Cl - This is possible, and the lower the amount of halogen residue in the thin film, the better the film quality and therefore preferable.

[0176] Further, the thin film has a residual halogen intensity (c / s) in the thin film based on a thin film thickness of 100 Å (10 nm) measured by SIMS (Secondary Ion Mass Spectrometry), which is preferably 100,000 or less, more preferably 90,000 or less, still more preferably 80,000 or less, and even more preferably 76,000 or less. In such a range, the effect of preventing corrosion and deterioration is excellent. Here, the halogen remaining in the thin film can be, for example, F2, F, or F - and it is preferable because the lower the halogen residue amount in the thin film, the better the film quality.

[0177] The thin film has, for example, 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.

[0178] The manufactured thin film can include one or two types from the group consisting of those of molybdenum, for example, specifically, molybdenum thin film, molybdenum nitride film (MoxNy, where 0 < x ≤ 1.2, 0 < y ≤ 1.2, preferably 0.8 ≤ x ≤ 1, 0.8 ≤ y ≤ 1, more preferably 1 respectively), and molybdenum oxide film (MozOw, where 0 < x ≤ 1.2, 0 < y ≤ 1.2, preferably 0.8 ≤ x ≤ 1, 0.8 ≤ y ≤ 1, more preferably 1 respectively). It can preferably include a molybdenum 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) of a semiconductor element.

[0179] Other metal thin films, metal nitride films, and metal oxide films presented in the present invention may also be applicable. For example, when an oxidizing agent such as oxygen or ozone is used as a reaction gas, the thin film represented by the following Chemical Formula 61 can be formed.

[0180] [[ID=I8]][Chemical Formula 61] (M1-aM”a)Ob

[0181] In Chemical Formula 61, a satisfies 0 ≦ a < 1, b satisfies 0 < b ≦ 2, and M is selected from atoms of Group 4 or titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge), tin (Sn), strontium (Sr), niobium (Nb), barium (Ba), or tantalum (Ta).

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

[0183] The lower layer film may be a dielectric film, and as an example, it may be formed by including 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, and TiO2.

[0184] The middle layer film may be formed by including, as an example, TixNy, preferably TiN.

[0185] The upper layer film may be formed by including one or more selected from the group consisting of W and Mo as an example.

[0186] Hereinafter, preferred examples and drawings are presented to assist in understanding the present invention. However, it is obvious to those skilled in the art that the following examples and drawings only illustrate the present invention, and various changes and modifications are possible within the scope of the present invention and the scope of the technical idea. It is natural that such variations and modifications belong to the appended claims.

[0187] [Examples] [Examples 1 to 5, Comparative Examples 1 to 3, Reference Examples 1 to 2] The combinations of growth regulators and metal thin film precursor compounds used in Examples 1-5, Comparative Examples 1-3, and Reference Examples 1-2 were selected from those shown in Table 1 below.

[0188] [Table 1]

[0189] <Examples 1-3> As growth regulators, tert-butyl iodide and MoO2Cl2 were prepared from the compounds listed in Table 1 as growth regulators and metal thin film precursor compounds, respectively. The prepared growth regulators and thin film precursor compounds were placed in canisters and supplied at room temperature to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller).

[0190] The growth regulator and thin-film precursor compound, vaporized in a vaporizer, were each introduced into the deposition chamber loaded with the substrate for 1 second in a 1:1 ratio. Argon purging was then performed by supplying argon gas at 5000 sccm for 2 seconds. During this process, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0191] Next, 1000 sccm of ammonia was added to the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 3 seconds. During this time, the substrate on which the metal thin film would be formed was heated to the temperatures shown in Table 2 below. This process was repeated 200 to 400 times to form a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0192] <Comparative Examples 1-3> Except for the case in Examples 1 to 3 in which no growth regulator was included, the same process as in Examples 1 to 3 was repeated.

[0193] As a result, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed.

[0194] <Example 4> In Example 1, the growth regulator and thin-film precursor compound, vaporized in a vaporizer, were sequentially introduced into a deposition chamber with a substrate loaded for 1 second each, in a 1:1 ratio. The process was repeated in the same manner as in Example 1, except that argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge.

[0195] Specifically, the growth regulator, vaporized in a vaporizer, was introduced into the deposition chamber with the substrate loaded for 1 second. After that, argon gas was supplied at 5000 sccm for 2 seconds for argon purging. Then, the metal thin film precursor compound, vaporized in a vaporizer, was introduced into the deposition chamber with the substrate loaded for 1 second. After that, argon gas was supplied at 5000 sccm for 2 seconds for argon purging.

[0196] As a result, after repeating the process 200 to 400 times, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed.

[0197] <Example 5> In the above-described Example 1, the growth regulator and thin-film precursor compound, vaporized into vapor form by a vaporizer, were sequentially introduced in a 1:1 ratio into a deposition chamber with a substrate loaded for 1 second each, and then argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge. The same process as in Example 1 was repeated.

[0198] Specifically, a metal thin film precursor compound vaporized in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds. Then, a growth regulator vaporized in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds.

[0199] As a result, after repeating the process 200 to 400 times, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed.

[0200] <Reference Example 1> In Example 1, the same steps as in Example 1 were repeated, except that tert-butyl iodide was replaced with 3-iodo butane as the growth regulator.

[0201] As a result, a MoN thin film with a self-limiting atomic layer thickness of 10 nm was formed.

[0202] [Experimental Example] 1) Evaporation evaluation (evaporation rate per cycle, GPC) For the fabricated thin film, the thickness of the thin film measured by an ellipsometer, which is a device capable of measuring optical properties such as the thickness and refractive index of the thin film using the polarization characteristics of light, was divided by the number of cycles to calculate the thickness of the thin film deposited per cycle, and the evaporation rate was evaluated. The results are shown in Table 2 below.

[0203] 2) Thin film resistance evaluation (specific resistance) The surface resistance of the fabricated thin film was measured by the four-point probe method to obtain the surface resistance, and then the specific resistance value was calculated from the thickness value of the thin film.

[0204] The improvement degree of the specific resistance (μΩ·cm) was calculated by the following formula 1.

[0205] [Formula 1] Specific resistance improvement degree (%) = [(Specific resistance when using the precursor composition - Specific resistance when not using the growth regulator) / Specific resistance when not using the growth regulator] X 100

[0206]

Table 2

[0207] As shown in Table 2 above, when the tert-butyl iodide of the present invention was used in combination with a thin film precursor compound as a growth regulator (Examples 1-3), it was shown that the resistivity decreased to 919-1884 μΩ·cm while providing an deposition rate equivalent to or similar to that when no growth regulator was used (Comparative Examples 1-3). This confirmed that the thin film growth rate was appropriately controlled and the electrical properties were improved.

[0208] 3) Impurity reduction characteristics To compare the impurity reduction characteristics, i.e., process by-products, of the manufactured 10 nm thick thin films, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the elements titanium (Ti), nitrogen (N), Cl (chlorine), carbon (C), and oxygen (O). The results are shown in Table 3 below.

[0209] [Table 3]

[0210] As shown in Table 3 above, when the growth regulator according to the present invention was used simultaneously with the thin film precursor compound (Example 1), it not only showed levels equivalent to or similar to the case where the growth regulator was not used (Comparative Example 1), but also showed that the intensity of both Cl and C was reduced to 0.01% compared to the case where other growth regulators were used (Reference Example 1), confirming excellent impurity reduction characteristics.

[0211] In particular, in Comparative Example 1, since no growth regulator was added, theoretically no carbon should have been detected. However, it was confirmed that carbon was detected, presumably originating from trace amounts of CO and / or CO2 contained in the thin film precursor compound, purge gas, and reaction gas. In contrast, in Example 1 of the present invention, despite adding a growth regulator, which is a hydrocarbon compound, during thin film deposition, it was confirmed that the carbon intensity decreased compared to Comparative Example 1. This means that the growth regulator of the present invention has excellent impurity reduction characteristics.

[0212] In particular, in Reference Example 1, a compound with a halide structure similar to the growth regulator of the present invention was added, but the impurity intensity was excessively high compared to Example 1 and, consequently, Comparative Example 1, confirming that there was no film quality improvement effect.

[0213] Furthermore, the following additional experiments were conducted to confirm the effects of growth regulators at different stages of injection.

[0214] <Additional Example 1> MoO2Cl2 was used as a Mo precursor, and ALD deposition evaluation was performed using a VFC supply method.

[0215] The canister heating temperature for MoO2Cl2 was 90°C, and deposition evaluation temperatures were set to 380°C, 400°C, and 420°C, respectively. The process pressure was 6 torr, and the flow rates of both the ammonia reaction gas and the Ar purge gas were 1000 sccm.

[0216] To confirm the improvement in resistivity and GPC, a MoN thin film was deposited and compared.

[0217] Specifically, two experiments were conducted: one in which MoO2Cl2 was injected, followed by Ar purging, then tert-butyl iodide was injected, followed by Ar, followed by NH3 reaction gas injection, and then Ar injection before ALD deposition (post-injection); and another in which tert-butyl iodide was injected, followed by Ar, then MoO2Cl2 was injected, followed by Ar, followed by NH3 reaction gas injection and then Ar injection before ALD deposition (pre-injection). After each experiment, the resistivity and deposition rate were measured using the method presented in the experimental example above. As a control group, the resistivity and deposition rate were also measured similarly for MoN thin films produced without the addition of growth regulators.

[0218] The results of each measurement are shown in Figure 1 below.

[0219] Figure 1 below is a diagram comparing an experiment in which the growth regulator presented in this invention was injected into MoO2Cl2 with a control experiment in which the growth regulator was not used.

[0220] As shown in Figure 1 below, the resistivity was reduced by 35% compared to the control group, and the deposition rate was increased by 34%.

[0221] Although specific measurement results are not attached, we confirmed that injecting the growth regulator tert-butyl iodide beforehand is superior to injecting it afterward in terms of improving resistivity.

[0222] <Additional Example 2> The same process as in Additional Example 1 was repeated, except that MoO2Cl2 was replaced with NbF5 to produce an NbN thin film.

[0223] The measurement results are shown in Table 4 and Figure 2 below.

[0224] Table 4 and Figure 2 below are diagrams comparing an experiment in which the growth regulator presented in this invention was pre-injected into NbF5 cells with a control group experiment in which the growth regulator was not used.

[0225] As shown in Table 4 and Figure 2 below, SIMS analysis confirmed that the levels of impurity fluorine (F impurity) and impurity carbon (C impurity) were improved compared to the control group and the NbN thin film.

[0226] [Table 4]

Claims

1. The product comprises a thin-film precursor compound and a growth regulator. The thin film precursor compound comprises a compound represented by the following chemical formula 1, The metal thin film precursor composition is characterized in that the growth regulator is a linear, branched, cyclic, or aromatic compound represented by the following chemical formula 2. [Chemical formula 1] MxNnLm (In the above chemical formula 1, x is an integer from 1 to 3, M can be selected from the group consisting of Nb, Mo, and W, n is an integer from 0 to 8, N is a ligand consisting of F, Cl, Br, or I, or a combination of two or more selected from the group consisting of F, Cl, Br, and I, m is an integer from 0 to 5, L is a ligand consisting of H, C, N, O, P, or S, or a combination of two or more selected from the group consisting of H, C, N, O, and P, and the compound represented by the above chemical formula 1 is selected from the compounds represented by the following chemical formulas 3 to 39.) [Chemical formula 2] AnBmXoYiZj (In the above chemical formula 2, A is carbon, silicon, nitrogen, phosphorus, or sulfur; B is hydrogen, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, or a C1-C10 alkoxy group; X is one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z are one or more independently selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine, and are not equal to each other; n is an integer from 1 to 15; o is an integer of 1 or more; m is 0 to 2n+1; and i and j are integers from 0 to 3.) [Chemical formula 3 to chemical formula 20] [Chemical formula 21 to chemical formula 31] [Chemical formula 32 to chemical formula 39] (In chemical formulas 3 to 39, the lines represent bonds, and no other elements are listed. The points where bonds intersect are carbon atoms, and the number of hydrogen atoms required to satisfy the valence of the carbon atoms is omitted. R' and R'' are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively, and R' can be linked to adjacent R' atoms.)

2. The metal thin film precursor composition according to claim 1, characterized in that in the chemical formula 1, n is an integer from 1 to 6.

3. The metal thin film precursor composition according to claim 1, characterized in that in the chemical formula 1, N is F, Cl or Br, or a ligand consisting of two or more types selected from the group consisting of F, Cl and Br.

4. The metal thin film precursor composition according to claim 1, characterized in that the growth regulator has a halide end group consisting of Cl, Br, or I, or a combination of two or more selected from the group consisting of Cl, Br, or I.

5. The metal thin film precursor composition according to claim 1, characterized in that the growth regulator is one or more compounds selected from those represented by the following chemical formulas 40 to 60. [Chemical formula 40 to chemical formula 60] (In chemical formulas 40 to 60 above, the lines represent bonds, and other elements are not listed. The points where bonds intersect represent carbon atoms, and the number of hydrogen atoms required to satisfy the valence of the carbon atoms has been omitted.)

6. The metal thin film precursor composition according to claim 1, characterized in that it is used in an atomic layer deposition (ALD) process, a plasma atomic layer deposition (PEALD) process, a chemical deposition (CVD) process, or a plasma chemical deposition (PECVD) process.

7. A method for forming a thin film, characterized by comprising the step of injecting the metal thin film precursor composition described in claim 1 into the interior of a chamber and adsorbing it onto the surface of a loaded substrate.

8. i) A step in which the growth regulator is vaporized and adsorbed onto the surface of the substrate loaded inside the chamber; ii) The step of primary purging the inside of the chamber with purge gas; iii) A step of vaporizing the thin film precursor compound inside the chamber and adsorbing it onto a surface different from the portion of the substrate on which the growth regulator is adsorbed, or binding it to the ends of the growth regulator adsorbed on the substrate; iv) The step of secondary purging the inside of the chamber with purge gas; v) The step of supplying the reaction gas inside the chamber; and vi) The thin film forming method according to claim 7, further comprising the step of tertiarily purging the inside of the chamber with a purge gas.

9. i-1) A step of vaporizing the growth regulator and thin film precursor compound of the metal thin film precursor composition, simultaneously injecting the vaporized growth regulator and thin film precursor compound into the chamber, adsorbing the growth regulator onto the surface of the substrate loaded into the chamber, adsorbing the thin film precursor compound onto a surface of the substrate different from the portion where the growth regulator is adsorbed, or binding the thin film precursor compound to the ends of the growth regulator adsorbed on the substrate; ii) The step of primary purging the inside of the chamber with purge gas; v) The step of supplying the reaction gas inside the chamber; and vi-1) The thin film forming method according to claim 7, further comprising the step of additionally purging the inside of the chamber with a purge gas.

10. i-2) A step in which the thin film precursor compound is vaporized and adsorbed onto the surface of the substrate loaded inside the chamber; ii) The step of primary purging the inside of the chamber with purge gas; iii) A step of vaporizing the growth regulator inside the chamber to adsorb the growth regulator onto a surface of the substrate different from the adsorbed portion, or to bind it to the ends of the thin film precursor adsorbed on the substrate; iv) The step of secondary purging the inside of the chamber with purge gas; v) The step of supplying the reaction gas into the chamber; and vi) The thin film forming method according to claim 7, further comprising the step of tertiarily purging the inside of the chamber with a purge gas.

11. The thin film formation method according to claim 7, characterized in that the metal thin film precursor composition is transferred into the interior of an ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber by a VFC, DLI, or LDS method.

12. The thin film formation method according to any one of claims 8 to 10, characterized in that the reaction gas is a reducing agent, a nitriding agent, or an oxidizing agent.

13. The thin film formation method according to claim 7, characterized in that the deposition temperature is 50 to 700°C.

14. The method for forming a thin film according to claim 7, characterized in that the thin film is an oxide film, a nitride film, or a metal film.

15. The thin film forming method according to claim 7, characterized in that the thin film includes a multilayer structure of two or three layers.

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