Thin film modification composition and method for forming a thin film using the same

Abstract

The present invention relates to a thin film modification composition, a thin film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. The thin film modification composition is composed of a film growth / film quality improving compound having a predetermined structure and a solvent having a specific dielectric constant, and by appropriately reducing the growth rate of a deposited film in a vacuum-based thin film process, even when a thin film is formed on a substrate having a complex structure, the step coverage and the film thickness uniformity of the thin film can be significantly improved, the etching efficiency can be improved, and impurity contamination can be significantly reduced.

Description

[Technical Field]

[0001] The present invention relates to a thin film modification composition, a thin film formation method using the same, a semiconductor substrate manufactured thereby, and a semiconductor device. More specifically, the present invention relates to a thin film modification composition comprising a film growth / film quality improvement compound of a predetermined structure and a solvent with a specified dielectric constant, which appropriately reduces the growth rate of the deposited film during a vacuum-based thin film process. This significantly improves step coverage and the uniformity of the film thickness, even when forming a thin film on a substrate with a complex structure, thereby improving the efficiency of the etching film and drastically reducing impurity contamination. The present invention also relates to a thin film modification composition, a thin film formation method using the same, and a semiconductor substrate manufactured thereby. [Background technology]

[0002] The increasing integration density of memory and non-memory semiconductor elements is leading to increasingly complex microstructures on substrates.

[0003] For example, the width and depth of the microstructure (hereinafter also referred to as the "aspect ratio") have increased to 20:1 or more, and even 100:1 or more. The larger the aspect ratio, the more difficult it becomes to form a uniform layer thickness along the complex microstructure plane.

[0004] As a result, the step coverage, which limits the thickness ratio of the deposited layers formed in the upper and lower parts of the microstructure in the depth direction, remains at a level of 90%, making it increasingly difficult for the electrical characteristics of the device to be expressed. Since 100% step coverage means that the thickness of the deposited layers formed in the upper and lower parts of the microstructure is the same, it is necessary to develop technology to make the step coverage as close to 100% as possible.

[0005] The thin film for semiconductors consists of a nitride film, a thin film, a metal film, and the like. Examples of nitride films include silicon nitride (SiN), titanium nitride (TiN), and tantalum nitride (TaN); examples of thin films include silicon oxide (SiO2), hafnium oxide (HfO2), and zirconium oxide (ZrO2); and examples of metal films include molybdenum film (Mo) and tungsten (W).

[0006] The aforementioned thin film is generally used as a diffusion barrier between the doped silicon layer of a semiconductor and interlayer wiring materials such as aluminum (Al) and copper (Cu). However, when a tungsten (W) thin film is deposited onto a substrate, it is used as an adhesion layer.

[0007] As mentioned above, in order for a thin film deposited on a substrate to have good and uniform physical properties, high step coverage of the thin film is essential. For this reason, atomic layer deposition (ALD), which utilizes surface reactions, is used more frequently than chemical vapor deposition (CVD), which mainly utilizes gas-phase reactions. However, problems still remain in achieving 100% step coverage.

[0008] When increasing the deposition temperature to achieve 100% step coverage, difficulties arise in achieving step coverage. Firstly, in a deposition process consisting of two types of materials—precursors and reactants—increasing the deposition temperature not only leads to a steep increase in the thin film growth rate (GPC: Growth Per Cycle), but even if the ALD process is performed at 300°C to mitigate the increase in GPC due to the increased deposition temperature, the deposition temperature will still increase during the process, making it difficult to call this a solution.

[0009] In addition, in order to realize a metal thin film with excellent film quality in a semiconductor device, a high-temperature process is required. Research results have been reported that increasing the atomic layer deposition temperature to 400 °C reduces the concentrations of carbon and hydrogen remaining in the thin film (see the paper in J. Vac. Sci. Technol. A, 35(2017) 01B130).

[0010] However, the higher the deposition temperature, the more difficult it is to ensure the step coverage rate. First, in the deposition process composed of two types of precursors and reactants, an increase in the deposition temperature may lead to a sharp increase in the growth rate per cycle (GPC) of the thin film. Also, in order to mitigate the increase in GPC due to the increase in deposition temperature, even if a known masking agent is applied, it has been confirmed that the GPC increases by about 10% at 300 °C. That is, when depositing at 360 °C or higher, it is difficult to expect the GPC reduction effect provided by the conventionally known masking agent.

[0011] Therefore, at present, there is a demand for the development of a thin film formation method that can effectively form a thin film with a complex structure even at high temperatures, has a low residual amount of impurities, and significantly improves film quality such as step coverage, film thickness uniformity, and electrical properties of the thin film, and a semiconductor substrate manufactured thereby.

Summary of the Invention

Problems to be Solved by the Invention

[0012] The present invention has been made to solve the above-described problems of the prior art, and provides a thin film modification composition composed of a film growth / film quality improvement compound having a predetermined structure and a solvent having a specified dielectric constant, and appropriately reduces the growth rate of a vapor-deposited film during a vacuum-based thin film process. Even when forming a thin film on a substrate having a complex structure, the step coverage and the film thickness uniformity of the thin film can be significantly improved, the efficiency of an etched film can be improved, and a thin film modification composition with significantly reduced impurity contamination, a thin film forming method using the same, a semiconductor substrate manufactured thereby, and a semiconductor device including the same are provided.

[0013] An object of the present invention is to improve the density and dielectric properties of a thin film by improving the crystallinity and oxidation fraction of the thin film.

[0014] The above object and other objects of the present invention can all be achieved by the present invention described below.

Means for Solving the Problems

[0015] In order to achieve the above object, the present invention provides a thin film modification composition characterized by including a liquid halogen compound having a vapor pressure of 1 torr (25 °C) or more and a nonpolar solvent having a dielectric constant of 25 or less.

[0016] The thin film can be a vacuum-based vapor-deposited film or a vacuum-based etched film.

[0017] The liquid halogen compound can be an alkyl halide having 1 to 10 carbon atoms.

[0018] The liquid halogen compound can have a refractive index of 1.40 to 1.60, 1.40 to 1.58, or 1.40 to 1.56.

[0019] The aforementioned liquid halogen compound may include compounds represented by the following chemical formulas 1-1 to 1-9 when the thin film is a deposited film.

[0020] [Chemical formula 1-1~1-9]

[0021] [ka]

[0022] The aforementioned liquid halogen compound may include compounds represented by the following chemical formulas 2-1 to 2-3 when the thin film is an etched film.

[0023] [Chemical formula 2-1~2-3]

[0024] [ka]

[0025] The liquid halogen compound can control the reaction surface of the aforementioned vapor-deposited film or etched film.

[0026]

[0027] In the present invention, the liquid halogen compound and a nonpolar solvent having a dielectric constant of 25 or less can be used in combination.

[0028] The dielectric constant is preferably 25 or less, more specifically 15 or less, and more preferably 10 or less. Within this range, it does not show reactivity with the aforementioned liquid halogen compound, thus maximizing the effect to be provided by the liquid halogen compound without adversely affecting the process.

[0029] The nonpolar solvent having a dielectric constant of 25 or less may, for example, be a hydrocarbon solvent, a halogen solvent, a heterocyclic solvent, or an alcohol solvent.

[0030] The nonpolar solvent having a dielectric constant of 25 or less may, as a specific example, be one or more selected from octane, 1,2-dichloroethane, dimethylethylamine, tetrahydrofuran, N,N-dimethylformamide, isobutyl alcohol, and ethyl alcohol.

[0031]

[0032] Furthermore, the present invention is

[0033] The steps include treating the surface of a substrate loaded into a chamber with the thin film modification composition of claim 1,

[0034] The process includes the steps of injecting a precursor compound and a reaction gas into a chamber in this order, and forming a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and under a vacuum of less than 760 torr,

[0035] The present invention provides a thin film formation method characterized in that the reaction gas is an oxidizing agent or a reducing agent.

[0036] The chamber may be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

[0037] The thin-film modification composition and the precursor compound can be transported into the chamber by a vapor flow control (VFC), direct liquid introduction (DLI), or liquid delivery system (LDS).

[0038] At this time, the heating temperature of the deposition transport line (hereinafter referred to as the "injection line") may be in the range of 25 to 200°C for the substrate.

[0039] The thin film may be an oxide film or a nitride film.

[0040] The reaction gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0041] The thin film may be a thin film in which one or more layers of metal selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd are laminated.

[0042] The thin film may be used as a diffusion prevention film, etching stop film, electrode film, dielectric film, gate insulating film, blocking thin film, or charge trap.

[0043]

[0044] Furthermore, the present invention is

[0045] The step includes injecting an etching material into a chamber to form a vacuum-based etching film on a substrate,

[0046] The present invention provides a thin film formation method characterized in that the etching material is one or more selected from Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0047] The chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0048] The thin-film modification composition and the precursor compound can be transported into the chamber by VFC, DLI, or LDS.

[0049] The etching material can be used in combination with Ar, H2, or O2.

[0050]

[0051] The thin film formation method using the thin film modification composition is:

[0052] i) A step of vaporizing the aforementioned thin film modification composition to form a modified region on the surface of a substrate loaded into a chamber,

[0053] ii) The method is characterized by comprising the step of primary purging the inside of the chamber with a purge gas.

[0054] The thin-film modification composition can be supplied by coating a substrate loaded into a chamber under temperature conditions of 20 to 800°C.

[0055] The liquid halogen compound and nonpolar solvent constituting the thin-film modification composition may be injected into the chamber separately, or they may be injected into the chamber in a pre-mixed state.

[0056]

[0057] The thin film formation method described above is

[0058] i) A step of vaporizing the aforementioned thin film modification composition to form a modified region on the surface of a substrate loaded into a chamber,

[0059] ii) A step of primary purging the inside of the chamber with a purge gas,

[0060] iii) A step of vaporizing the precursor compound and adsorbing it onto the region outside the modified region,

[0061] iv) The step of secondary purging the inside of the chamber with purge gas,

[0062] v) The step of supplying a reaction gas to the inside of the chamber,

[0063] vi) A thin film formation method is provided, characterized by comprising the step of tertiarily purging the inside of the chamber with a purge gas.

[0064] The thin-film modification composition can be supplied by coating a substrate loaded into a chamber under temperature conditions of 20 to 800°C.

[0065] The liquid halogen compound and nonpolar solvent constituting the thin-film modification composition may be injected into the chamber separately, or they may be injected into the chamber in a pre-mixed state.

[0066] The precursor compound is a molecule composed of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may be a precursor having a vapor pressure at 25°C greater than 0.01 mTorr and less than or equal to 100 torr.

[0067] The thin-film modification composition or precursor compound may be vaporized and injected, followed by a plasma post-treatment step.

[0068] In steps ii) and iv), the amount of purge gas introduced into the chamber can be 10 to 100,000 times the volume of the introduced thin-film modification composition or precursor compound.

[0069] The reaction gas is an oxidizing agent or a reducing agent, and the reaction gas, thin film modification composition, and precursor compound can be transported into the chamber by VFC, DLI, or LDS.

[0070] The substrate loaded into the chamber is heated to 100-800°C, and the ratio of the amount (mg / cycle) of the thin-film modification composition to the precursor compound introduced into the chamber may be 1:1-1:20.

[0071]

[0072] Furthermore, the present invention provides a semiconductor substrate characterized by including a thin film manufactured by the thin film formation method described above.

[0073] The thin film may have a multilayer structure consisting of two or three or more layers.

[0074] Furthermore, the present invention provides a semiconductor device including the aforementioned semiconductor substrate.

[0075] 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) capacitor, or a 3D NAND flash memory. [Effects of the Invention]

[0076] According to the present invention, by using a thin film modification composition comprising a film growth / film quality improvement compound of a predetermined structure and a solvent with a specified dielectric constant during a vacuum-based thin film process, the growth rate of the deposited film can be appropriately reduced during the vacuum-based thin film process. This significantly improves step coverage and film thickness uniformity, even when forming a thin film on a substrate with a complex structure, thereby improving the efficiency of etching films and providing a thin film modification composition that can drastically reduce impurity contamination.

[0077] Furthermore, this method has the effect of further reducing process by-products during thin film formation, preventing corrosion and degradation, and improving the crystallinity of the thin film by modifying its properties, thereby improving its electrical properties.

[0078] Furthermore, by reducing process by-products, lowering the reaction rate, and appropriately decreasing the thin film growth rate during thin film formation, it is possible to improve step coverage and thin film density even when forming thin films on substrates with complex structures. Moreover, it is possible to provide a thin film formation method using this method and a semiconductor substrate manufactured therefrom. [Brief explanation of the drawing]

[0079] [Figure 1] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of thin film modification compositions. The graph shows a thin film obtained using 2-chloro-2-methylbutane alone (top) and a thin film obtained using a 1:1 molar mixture of 2-chloro-2-methylbutane and octan (bottom). [Figure 2] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of thin film modification compositions. The graph shows a thin film obtained using iodocyclopentane alone (top) and a thin film obtained using a 1:1 molar mixture of iodocyclopentane and 1,2-dichloroethane (bottom). [Figure 3] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of thin-film modification compositions. The graphs show thin films obtained using 1-chloro-1-methylcyclohexane alone (top) and thin films obtained using a 1:1 molar mixture of 1-chloro-1-methylcyclohexane and octane (bottom), respectively. [Modes for carrying out the invention]

[0080] The thin-film modification composition described herein, the thin-film formation method using the same, and the semiconductor substrate manufactured therefrom will be described in detail below.

[0081] In this description, unless otherwise specified, the term "thin film modification" refers to controlling the surface of the substrate used as the surface chemical reaction surface in the vapor deposition process.

[0082] In this description, the term "film growth / film quality improvement" means, unless otherwise specified, improving film growth by reducing, preventing, or blocking the adsorption of precursor compounds for forming thin films onto the substrate, as well as reducing, preventing, or blocking the adsorption of process by-products onto the substrate, or improving film quality such as electrical properties and thin film density.

[0083] In this description, known values ​​in this field (calculated values ​​at 20°C) can be used as dielectric constants. https: / / macro.lsu.edu / howto / solvents / Dielectric%20Constant%20.htm reference).

[0084] The inventors have found that by modifying the surface of a substrate during a vacuum-based deposition or etching process, and using a film growth / film quality improvement compound with a predetermined structure and a solvent with a specified dielectric constant as a thin film modification composition to improve the deposition or etching process, the growth rate of the deposited film can be appropriately reduced. This significantly improves step coverage and film thickness uniformity, even when forming a thin film on a substrate with a complex structure, and improves the efficiency of the etched film. In particular, it enables deposition at a thin thickness and improves residual O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce as process by-products. Based on this finding, the inventors incorporated research on film growth / film quality improvement compounds to complete the present invention.

[0085]

[0086] The thin film modification composition of the present invention may be applied to vacuum-based deposited films or vacuum-based etched films.

[0087] The aforementioned deposited film or etched film can be provided, for example, as one or more precursors selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and can provide a modification region for oxide films, nitride films, metal films, or selective thin films thereof, in which case the effects to be achieved in the present invention can be fully obtained.

[0088] The thin film may, as a specific example, have a film composition of a silicon oxide film or a silicon nitride film.

[0089] The aforementioned thin film can be used not only as a diffusion prevention film for general purposes, but also in semiconductor devices for applications such as etching stop films, electrode films, dielectric films, gate insulating films, block thin films, or charge traps.

[0090]

[0091] In the present invention, as an example of a precursor compound used to form a thin film, the compound represented by the following chemical formula 3 can be used.

[0092] [Chemical formula 3]

[0093] [ka]

[0094] (In the above chemical formula 3, M is one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, L 1 , L 2 , L 3 and L 4 -H, -X, -R, -OR, -NR 2or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br, or I, and -R is an alkyl of C1~C 10 an alkene of C1~C 10 or an alkane of C1~C 10 which may be linear or cyclic, and the L 1 , L 2 , L 3 and L 4 can be formed to be 2~6 according to the oxidation state of the central metal. )

[0095] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as ligands. When the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and the ligands corresponding to L 1 ~L 6 may be the same or different from each other.

[0096] The M can be a species corresponding to a trivalent metal, a tetravalent metal, a pentavalent metal or a hexavalent metal, preferably hafnium (Hf), zirconium (Zr), aluminum (Al), niobium (Nb), or tantalum (Ta). In this case, there are advantages such as a large effect of reducing process by-products, excellent step coverage, an effect of improving the thin film density, and further excellent electrical properties, insulation and dielectric properties of the thin film.

[0097] The L 1 , L 2 , L 3 and L 4 are -R, -X or Cp, which may be the same or different from each other, where -R is an alkyl of C1~C 10 an alkene of C1~C 10 or an alkane of C1~C 10 which may have a linear or cyclic structure.

[0098] Furthermore, the L 1 , L 2 , L 3 and L 4 -NR 2 or Cp, which may be the same or different from each other, where -R is H, C1-C10 alkyl, C1-C 10 Alkenes, C1~C 10 It could be an alkane, iPr, or tBu.

[0099] Furthermore, in the above chemical formula 3, L 1 , L 2 , L 3 and L 4 -H or -X, which may be the same or different from each other, where -X may be F, Cl, Br, or I.

[0100] Specifically, suitable aluminum precursor compounds include, for example, Al(CH3)3 and AlCl4.

[0101] Furthermore, examples of hafnium precursor compounds that can be used include tris(dimethylamide)cyclopentadienylhafnium (CpHf(NMe2)3) and (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium (Cp(CH2)3NM3Hf(NMe2)2).

[0102] Examples of silicon precursor compounds that can be used include hexachlorodisilane (HCDS), dichlorosilane (DCS), tris(dimethylamino)silane (3DMAS), bis(diethylamino)silane (BDEAS), and octamethylcyclotetrasiloxane (OMCTS).

[0103]

[0104] The thin-film modification composition of the present invention allows for the control of vacuum-based thin-film growth and film quality by pre-controlling the surface on the substrate where the precursor compound should be adsorbed, thereby reducing the rate at which the precursor compound is adsorbed onto the substrate.

[0105] The thin film modification composition may include a liquid halogen compound having a vapor pressure of 1 torr (25°C) or higher and a non-polar solvent having a dielectric constant of 25 or less. In this case, side reactions are suppressed during the formation of a vapor-deposited or etched film, the thin film growth rate is adjusted, process by-products within 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, step coverage and uniformity of the thin film thickness are greatly improved while minimizing contamination by impurities.

[0106] As a specific example, the halogen compound may have a refractive index in the range of 1.40 to 1.60, 1.40 to 1.58, or 1.40 to 1.56. In this case, the effect of reducing process by-products is significant, the step coverage is excellent, and the effect of improving thin film density and the electrical properties of the thin film are even better.

[0107] The liquid halogen compound is preferably used in an atomic layer deposition (ALD) process, which has the advantage of effectively protecting the substrate surface and effectively removing process by-products without hindering the adsorption of precursor compounds or etching by etching materials.

[0108] The liquid halogen compound is preferably 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 3 The vapor pressure (at 20°C) can be between 0.1 and 300 mmHg or between 1 and 300 mmHg. Within this range, a modified region is effectively formed, resulting in excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0109] More preferably, the liquid halogen compound has a density of 0.75 to 2.0 g / cm³. 3 Or 0.8-1.3 g / cm³ 3 Therefore, the vapor pressure (at 20°C) can be between 1 and 260 mmHg, and within this range, it effectively forms a modified region, resulting in excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0110] The liquid halogen compound is preferably used in an atomic layer etching (ALE) process. In this case, since chemical etching is used, it has the effect of achieving selective etching and isotropic etching characteristics of the etched film to be provided.

[0111]

[0112] The aforementioned liquid halogen compound, by containing alkyl halides having 1 to 10 carbon atoms, exhibits a significant reduction in process by-products, excellent step coverage, and further superior thin film density and electrical properties.

[0113] The halogen contained in the alkyl halide may be fluorine, bromine, chlorine, or iodine, and at least one of these may be included in the alkyl halide. In this case, there is a significant reduction in process by-products, excellent step coverage, and further advantages in improving thin film density and the electrical properties of the thin film.

[0114]

[0115] The liquid halogen compound, when the thin film is a vapor-deposited film, is preferably one or more compounds selected from those represented by the following chemical formulas 1-1 to 1-9. In this case, when forming the vapor-deposited film, a relatively rough thin film is formed, side reactions are suppressed, the thin film growth rate is adjusted, process by-products within 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, not only are step coverage and thickness uniformity of the thin film greatly improved, but contamination by impurities can be minimized.

[0116] [Chemical formula 1-1~1-9]

[0117] [ka]

[0118] When the thin film is an etched film, the liquid halogen compound is preferably a compound represented by the following chemical formulas 2-1 to 2-3, in which case the etching process can be effectively carried out while minimizing contamination by impurities.

[0119] [Chemical formula 2-1~2-3]

[0120] [ka]

[0121]

[0122] While the aforementioned liquid halogen compounds can be used alone, it is preferable to use them in combination with specific organic solvents, considering the harsh atmosphere under a vacuum base, as this allows for more efficient processing.

[0123] In this case, it is preferable to use an organic solvent with a dielectric constant of 15 or less, as this does not affect the reaction mechanism of the aforementioned liquid halogen compound under vacuum and improves the process.

[0124] Examples of nonpolar solvents having a dielectric constant of 25 or less include hydrocarbon solvents, halogenated solvents (excluding the aforementioned liquid halogenated compounds), heterocyclic solvents, and alcoholic solvents.

[0125] The hydrocarbon solvent may be a linear hydrocarbon compound having an alkyl group with 1 to 10 carbon atoms, and as an example, octane (d: 1.9 at 25°C) can be used.

[0126] The halogenated solvent may be a linear hydrocarbon compound substituted with terminal halogens, where at least one, preferably two or more, halogens are substituted. For example, 1,2-dichloroethane (d: 10.7 at 25°C) can be used.

[0127] The heterocyclic solvent may contain nitrogen or oxygen.

[0128] Examples of the nitrogen-containing solvent include dimethylethylamine (d:3.2 at 25°C).

[0129] Examples of the oxygen-containing solvent include tetrahydrofuran (d:7.6 at 25°C).

[0130] Examples of the aforementioned alcohol-based solvents include isobutyl alcohol (d: 16.68 at 25°C) and ethyl alcohol (d: 24.55 at 25°C).

[0131]

[0132] As a specific example, the vacuum-based thin film modification composition may contain one or more compounds selected from the compounds represented by the aforementioned chemical formulas 1-1 to 1-9, along with a non-polar solvent having a dielectric constant of 25 or less. In this case, it has a significant effect in adjusting the growth rate of the deposited film, a significant effect in removing process by-products, and outstanding effects in improving step coverage and film quality. Moreover, even when applied to substrates with complex structures, it ensures thin film uniformity and greatly improves step coverage. In particular, it can be deposited on thin films and can improve residual O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce. Even when manufacturing etched films, it can provide an improvement in film quality.

[0133] The reaction gas may include O2, NH3, or H2.

[0134] The thin film may be a thin film in which one or more layers of metal selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd are laminated.

[0135] The thin film modification composition can provide a modification region for thin films.

[0136] The thin film modification composition is characterized by not remaining on the thin film.

[0137] In this context, "no residue" means, unless otherwise specified, the presence of C, Si, N, and halogen elements in amounts less than 0.1 atomic%, less than 0.1 atomic%, less than 0.1 atomic%, or less than 0.1 atomic%, when analyzing the components by XPS. More preferably, in a measurement method using secondary-ion mass spectrometry (SIMS) or X-ray photoelectron spectroscopy (XPS) while measuring while drilling into the substrate in the depth direction, when considering the increase or decrease in C, N, Si, and halogen impurities before and after using the thin-film modification composition under the same deposition conditions, it is preferable that the increase or decrease in the signal intensity of each element does not exceed 5%.

[0138] The thin film may, for example, contain a halogen compound at a concentration of 100 ppm or less.

[0139] The thin film can be used, but is not limited to, as a diffusion prevention film, etching stop film, electrode film, dielectric film, gate insulating film, blocking thin film, or charge trap.

[0140] The liquid halogen compound, organic solvent, and precursor compound may preferably be compounds with a purity of 99.9% or higher, 99.95% or higher, or 99.99% or higher. For reference, if a compound with a purity of less than 99% is used, there is a risk that impurities may remain in the thin film or cause side reactions with the precursor or reactants. Therefore, it is preferable to use a substance with a purity of 99% or higher whenever possible.

[0141]

[0142] The present invention provides a thin film formation method comprising the steps of: treating the surface of a substrate loaded into a chamber with the aforementioned thin film modification composition; and injecting a precursor compound and a reaction gas into the chamber in that order to form a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and a vacuum of less than 760 torr, wherein the reaction gas is an oxidizing agent or a reducing agent. In this case, the deposition rate of the thin film on the substrate is reduced, and the thin film growth rate is appropriately lowered. This has the effect of significantly improving step coverage and thin film thickness uniformity while minimizing contamination by impurities, even when forming a thin film on a substrate with a complex structure.

[0143] In the step of treating with the thin film modification composition, the feeding time (seconds (sec)) of the thin film modification composition to the surface of the substrate is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 5 seconds per cycle. Within this range, there is an advantage that the thin film growth rate is low, the step coverage and economy are excellent, and impurity contamination can be minimized.

[0144] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle at a chamber volume of 15 to 20 L, and more specifically, on a flow rate of 0.8 to 200 mg / cycle at a chamber volume of 18 L.

[0145]

[0146] The thin film modification method of the present invention may include the steps of: i) vaporizing the aforementioned thin film modification composition to form a modified region on the surface of a substrate loaded into a chamber; and ii) primary purging the inside of the chamber with a purge gas.

[0147] The thin film modification method, and further the thin film formation method, may, as a preferred embodiment, include: i) vaporizing the thin film modification composition and treating the surface of a substrate loaded into a chamber; ii) primary purging the inside of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it onto the surface of a substrate loaded into the chamber; iv) secondary purging the inside of the chamber with a purge gas; v) supplying a reaction gas to the inside of the chamber; and vi) tertiary purging the inside of the chamber with a purge gas.

[0148] In this case, steps i) to vi) can be considered as a unit cycle, and the cycle can be repeated until a thin film of the desired thickness is obtained. When the thin film modification composition of the present invention is added to the substrate before the precursor compound within one cycle and adsorbed onto it, even when deposition is performed at high temperatures, the thin film growth rate can be appropriately reduced, the process by-products generated are effectively removed, the resistivity of the thin film decreases, and the step coverage is greatly improved.

[0149] In another preferred embodiment, the substrate may be manufactured by coating the thin-film modification composition onto a substrate loaded into a chamber under temperature conditions of 20 to 800°C.

[0150] In the thin film formation method of the present invention, as a preferred example, the thin film modification composition of the present invention can be introduced before the precursor compound within one cycle to activate the substrate surface, and then the precursor compound can be introduced and adsorbed onto the substrate. In this case, even if the thin film is deposited at high temperatures, the thin film growth rate can be appropriately reduced, process by-products can be significantly reduced, step coverage can be greatly improved, the crystallinity of the thin film can be increased and the resistivity of the thin film can be reduced. Even when applied to semiconductor devices with a large aspect ratio, the uniformity of the film thickness can be greatly improved, ensuring the reliability of the semiconductor device.

[0151]

[0152] As an example, in the thin film formation method, when the thin film modification composition is deposited before or after the deposition of the 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 while fully achieving the effects to be achieved in the present invention.

[0153]

[0154] The precursor compound is a molecule having one or more central metal atoms (M) selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and one or more ligands consisting of C, N, O, H, X (halogen), and Cp (cyclopentadiene), and the precursor has a vapor pressure of 1 mTorr to 100 torr at 25°C. In such cases, the effect of forming a modified region by the thin film modification composition described above can be maximized, even in the event of spontaneous oxidation.

[0155] In the present invention, the chamber may, for example, be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0156] The thin film may be a silicon oxide film, a silicon nitride film, a titanium oxide film, a titanium nitride film, a hafnium oxide film, a hafnium nitride film, a zirconium oxide film, a zirconium nitride film, a tungsten oxide film, a tungsten nitride film, an aluminum oxide film, an aluminum nitride film, a niobium oxide film, a niobium nitride film, a tellurium oxide film, or a tellurium nitride film.

[0157] In the present invention, the liquid halogen compound or precursor compound may be vaporized and injected, followed by a plasma post-treatment step, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0158]

[0159] When the thin-film modification composition is first adsorbed onto the substrate, followed by the adsorption of the precursor compound, and then the adsorption of the precursor compound, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed thin-film modification agent or thin-film modification composition is not particularly limited as long as it is sufficient to remove the unadsorbed thin-film modification composition. For example, it may 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 thin-film modification composition can be sufficiently removed to form a uniform thin film and prevent deterioration of the film quality. Here, the amounts of purge gas and thin-film modification composition introduced are based on one cycle, and the volume of the thin-film modification composition refers to the volume of vaporized thin-film modification composition, or the volume of vaporized liquid halogen compound and nonpolar solvent vapors, respectively.

[0160] As a specific example, if the injection amount of the thin film modification composition is 200 sccm, and in the step of purging the unadsorbed thin film modification composition, the flow rate of the purge gas is 5000 sccm, then the injection amount of purge gas is 25 times the injection amount of the thin film modification composition.

[0161]

[0162] Furthermore, in the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the chamber is not particularly limited as long as it is sufficient to remove the unadsorbed precursor compound. For example, it may be 10 to 10,000 times the volume of the precursor compound introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed precursor compound can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of purge gas and precursor compound introduced are based on one cycle, and the volume of the precursor compound refers to the volume of vaporized precursor compound vapor.

[0163]

[0164] Furthermore, in the purging step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the chamber may, for example, be 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 within this range, the desired effect can be sufficiently obtained. Here, the amounts of purge gas and reaction gas introduced are based on one cycle each.

[0165]

[0166] The thin-film modification composition and precursor compound may be transported into the chamber by VFC, DLI, or LDS, and more preferably by LDS.

[0167] The liquid halogen compound and nonpolar solvent constituting the thin film modification composition may be transported separately into the chamber, or they may be transported together in a combined state.

[0168] The substrate loaded into the chamber may be heated to, for example, 100 to 650°C, and more specifically, 150 to 550°C. The thin-film modification composition or precursor compound may be injected onto the substrate either unheated or heated. Depending on the deposition efficiency, the mixture may be injected unheated first, and then the heating conditions may be adjusted during the deposition process. For example, it can be injected onto the substrate at 100 to 650°C for 1 to 20 seconds.

[0169]

[0170] The ratio of the amount (mg / cycle) of the precursor compound to the thin-film modification composition introduced into the chamber is preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and reducing process by-products is significant.

[0171]

[0172] As an example, when the thin film formation method uses the thin film modification composition and the precursor compound, the deposition rate reduction rate represented by the following formula 1 may be 20% or more, preferably 50% or more. In this case, by using the film growth / film quality improvement compound or thin film modification composition having the aforementioned structure, a relatively rough thin film is formed, and the growth rate of the formed thin film is significantly reduced. Even when applied to substrates with complex structures at high temperatures, the uniformity of the thin film is ensured, the step coverage is greatly improved, and in particular, it is possible to deposit thin films. Furthermore, it is possible to improve the amount of O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce as process by-products.

[0173] [Formula 1]

[0174] Evaporation rate reduction rate = [{(DR i )-(DR f )} / (DR i )] × 100

[0175] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which the thin film is deposited. When a thin film formed by a precursor and reactants is deposited, DR i (Initial Deposition Rate) is the deposition rate of a thin film formed without the addition of a thin film modification composition. f The (final Deposition rate) is the deposition rate of the thin film formed by adding the thin film modification composition during the process described above. Here, the deposition rate (DR) is measured using an ellipsometer for thin films with a thickness of 3 to 30 nm under normal temperature and pressure conditions, and is measured in Å / cycle units.

[0176] In the above formula 1, the thin film growth rate per cycle when the thin film modification composition is used and when it is not used refers to the deposited film thickness (Å / cycle) of the thin film per cycle, i.e., the deposition rate. As an example, the deposition rate can be determined by measuring the final thickness of a thin film with a thickness of 3 to 30 nm using ellipsometry under room temperature and atmospheric pressure conditions, and then dividing by the total number of cycles to obtain the average deposition rate.

[0177] In the aforementioned formula 1, "when the thin film modification composition is not used" means the case in which only the precursor compound is adsorbed onto the substrate during the thin film deposition process to produce the thin film. A specific example is the case in which the thin film is formed by omitting the step of adsorbing the thin film modification composition and the step of purging the unadsorbed thin film modification composition from the thin film formation method.

[0178]

[0179] The thin film formation method described above allows the residual halogen intensity (c / s) in the thin film, measured based on SIMS and based on a thin film thickness of 100 Å / cycle, to be preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred embodiment, it may be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and deterioration is outstanding.

[0180] In this description, the purging is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeters 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, and deposition is performed as a single atomic layer (atomic mono-layer) or approximately thereof, which has the advantage of being advantageous in terms of film quality.

[0181]

[0182] The aforementioned ALD (atomic layer deposition process) is highly advantageous for the fabrication of integrated circuits (ICs) that require a high aspect ratio. In particular, its self-limiting thin film growth mechanism offers advantages such as excellent conformality, uniformity, and high-precision thickness control.

[0183] The aforementioned thin film formation method can, for example, be carried out at an evaporation temperature in the range of 50 to 800°C, preferably in the range of 300 to 700°C, more preferably in the range of 400 to 650°C, even more preferably in the range of 400 to 600°C, and even more preferably in the range of 450 to 600°C. Within this range, it is possible to grow a thin film with excellent film quality while achieving the ALD process characteristics.

[0184] The aforementioned thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 torr, preferably in the range of 0.1 to 20 torr, more preferably in the range of 0.1 to 10 torr, and most preferably in the range of 0.3 to 7 torr. Within this range, a thin film with a uniform thickness can be obtained.

[0185] In this description, the deposition temperature and deposition pressure may be measured as the temperature and pressure formed within the deposition chamber, or as the temperature and pressure applied to the substrate within the deposition chamber.

[0186] The thin film formation method may preferably include the step of raising the temperature inside the chamber to the deposition temperature before introducing the precursor compound into the chamber, and / or the step of purging the chamber by injecting an inert gas into the chamber before introducing the precursor compound into the chamber.

[0187] Furthermore, the present invention may include a thin film manufacturing apparatus capable of realizing the thin film manufacturing method, comprising an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transport means for transporting the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second transport means for transporting the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the art to which the present invention belongs.

[0188] The heating temperature of the deposition transport means (hereinafter referred to as the "injection line") may be in the range of 25 to 200°C for the substrate, and the reaction gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0189]

[0190] According to another aspect of the present invention, a thin film formation method can be provided, comprising the steps of treating the surface of a substrate loaded into a chamber with the aforementioned thin film modification composition, and injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate, wherein the etching substance is one or more selected from Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0191] The etching material can be used in combination with Ar, H2, or O2. Aside from this, specific details regarding matters that overlap with the formation of the deposited film are omitted.

[0192]

[0193] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described herein, and in such a case, the step coverage and uniformity of the film thickness of the thin film are significantly superior, and the density and electrical properties of the thin film are also excellent.

[0194] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 0.5 to 20 nm, more preferably 1.5 to 15 nm, and even more preferably 2 to 10 nm, and within this range, it has the effect of exhibiting excellent thin film properties.

[0195] The thin film may have a carbon impurity content of preferably 5,000 counts / sec or less, or 1 to 3,000 counts / sec, more preferably 10 to 1,000 counts / sec, and even more preferably 50 to 500 counts / sec. Within this range, it has the effect of reducing the thin film growth rate while maintaining excellent thin film properties.

[0196] As an example, the aforementioned thin film has a step coverage rate of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even if the thin film has a complex structure, it can be easily deposited onto a substrate, which has the advantage of being applicable to next-generation semiconductor devices.

[0197] Preferably, the manufactured thin film has a film thickness of 20 nm or less, a dielectric constant of 5 to 29 relative to a film thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage ratio of 90% or more. Within this range, it exhibits excellent performance as a dielectric film or blocking film, but is not limited to this.

[0198]

[0199] The thin film may, as an example, be a multilayer structure of two or three or more layers, preferably a multilayer structure of two or three layers, as needed. The two-layer multilayer film may, as a specific example, be a lower layer-middle layer structure, and the three-layer multilayer film may, as a specific example, be a lower layer-middle layer-upper layer structure.

[0200] The aforementioned underlayer film may, for example, consist of one or more elements selected from the group consisting of Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0201] The aforementioned intermediate layer is, as an example, Ti xN y Preferably, it may include TN.

[0202] The aforementioned upper layer may, for example, comprise one or more elements selected from the group consisting of W and Mo.

[0203] 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) capacitor, or a 3D NAND flash memory.

[0204]

[0205] The following examples and drawings are provided to further the understanding of the present invention. However, these examples and drawings are merely illustrative of the present invention, and it will be obvious to those skilled in the art that a wide variety of changes and modifications can be made within the scope of the present invention and the technical concept. It goes without saying that such modifications and changes also fall within the scope of the attached claims.

[0206]

[0207] [Examples]

[0208] <Test Example 1>

[0209] Examples 1-4, Comparative Example 1, Reference Examples 1-2

[0210] For the experiment, the following compounds, each with a dielectric constant of 15 or less, were mixed in a 1:1 molar ratio with the compounds represented by chemical formulas 1-1, 1-4, and 1-7, respectively: the compound represented by chemical formula 4-1 (d: 1.9 at 25°C), the compound represented by chemical formula 4-2 (d: 3.2 at 25°C), the compound represented by chemical formula 4-3 (d: 7.6 at 25°C), the compound represented by chemical formula 4-4 (d: 10.7 at 25°C), the compound represented by chemical formula 4-5 (d: 16.7 at 25°C), the compound represented by chemical formula 4-6 (d: 24.6 at 25°C), and the compound represented by chemical formula 4-7 (d: 36.7 at 25°C). 1 The degree of reactivity was confirmed by the presence or absence of novel impurity peaks using 1H-NMR.

[0211] [Chemical formula 4-1]

[0212] [ka]

[0213] [Chemical formula 4-2]

[0214] [ka]

[0215] [Chemical formula 4-3]

[0216] [ka]

[0217] [Chemical formula 4-4]

[0218] [ka]

[0219] [Chemical formula 4-5]

[0220] [ka]

[0221] [Chemical formula 4-6]

[0222] [ka]

[0223] [Chemical formula 4-7]

[0224] [ka]

[0225] [Chemical formula 1-1]

[0226] [ka]

[0227] [Chemical formula 1-4]

[0228] [ka]

[0229] [Chemical formula 1-7]

[0230] [ka]

[0231] *The results obtained are summarized in Table 1 and Figures 1 to 3 below. Here, if a new impurity peak is observed, it is considered to be reactive and is indicated by O, and if no new impurity peak is observed, it is considered to be unreactive and is indicated by X.

[0232] [Table 1]

[0233] As is clear from Table 1 and Figures 1 to 3 below, in Examples 1 to 4, which incorporate compounds represented by chemical formulas 4-1, 4-2, 4-3, and 4-4, each with a dielectric constant of 15 or less, no reactivity was observed regardless of the type of liquid halogen compound, and it is recognized that this is effective in improving the vapor deposition process. On the other hand, in Reference Example 1, which incorporates a compound represented by chemical formula 4-5, each with a dielectric constant slightly exceeding 15, no reactivity was observed in the case of iodocyclopentane, and it is recognized that this is suitable for improving the vapor deposition process depending on the type of liquid halogen compound.

[0234] On the other hand, Reference Example 2, which incorporates a compound represented by chemical formula 4-6 with a dielectric constant slightly exceeding 15, was observed to be unreactive in the case of iodocyclopentane, and is considered suitable for improving the deposition process depending on the type of liquid halogen compound.

[0235] In contrast, in the case of Comparative Example 1, which incorporates a compound represented by chemical formula 4-7 with a dielectric constant far exceeding 25, reactivity was observed regardless of the type of liquid halogen compound, and it was deemed unsuitable for improving the vapor deposition process.

[0236]

[0237] <Test Example 2>

[0238] The ALD deposition process was carried out using the components and steps shown in Table 1.

[0239] Specifically, in Table 1 below, for the SiN deposition of Comparative Example 1-1, a hexachlorodisilane (HCDS) precursor was used, with the canister heating temperature set to 35°C, the N2 carrier gas flow rate set to 40 sccm for 3 seconds, the NH3 flow rate set to 1000 sccm for 30 seconds, and the N2 purge gas flow rate set to 1000 sccm for 12 seconds. This process was repeated 100 to 150 times.

[0240] During this process, the canister heating temperature was maintained at 50°C, and the N2 carrier gas flow rate was maintained at 100 sccm for 3 seconds. Furthermore, the process of injecting the substances represented by chemical formulas 1-1, 1-4, and 1-7 separately for 3 seconds each was repeated 100 to 150 times.

[0241] Specifically, the substances represented by chemical formulas 1-1, 1-4, and 1-7 were mixed in a 1:1 molar ratio with the compositions shown in Table 1 from among the organic solvents represented by chemical formulas 4-1 to 4-6, respectively, and a liquid delivery system (LDS) was used.

[0242] The thin films obtained in Examples 1-4, Comparative Example 1, and Reference Examples 1-2 were analyzed for their 10 nm SiN film thickness by ellipsometry.

[0243] Furthermore, for the thin films obtained in Examples 1-4, Comparative Example 1, and Reference Examples 1-2, the film thickness of the SiN thin film deposited to a thickness of 10 nm was measured by ellipsometry optical analysis fitting, and the deposition rate of film thickness per cycle (Å / cycle) was measured by dividing the obtained film thickness by the total ALD cycle.

[0244] As a result, it was confirmed that the deposition rate was reduced by 20% or more in Examples 1 to 4 compared to Comparative Example 1. In contrast, in Reference Examples 1 to 2, it was confirmed that the deposition rate was reduced by 20% or more only when the compounds represented by chemical formulas 1-7 were used.

Claims

1. A thin film modification composition, A liquid halogen compound having a vapor pressure of 1 torr (25°C) or higher, A nonpolar solvent having a dielectric constant of 25 or less, Includes, The thin film modification composition is characterized in that the liquid halogen compound includes a compound represented by the following chemical formulas 1-1 to 1-9 when the thin film is a vapor-deposited film, and includes a compound represented by the following chemical formulas 2-1 to 2-3 when the thin film is an etched film. [Chemical formulas 1-1 to 1-9] 【Chemistry 1】 [Chemical formulas 2-1 to 2-3] 【Chemistry 2】

2. The vacuum-based thin-film modification composition according to claim 1, characterized in that the nonpolar solvent having a dielectric constant of 25 or less is a halogen-based solvent, a heterocyclic solvent, or an alcohol-based solvent.

3. The vacuum-based thin-film modification composition according to claim 2, characterized in that the nonpolar solvent having a dielectric constant of 25 or less is one or more selected from octane, 1,2-dichloroethane, dimethylethylamine, tetrahydrofuran, N,N-dimethylformamide, isobutyl alcohol, and ethyl alcohol.

4. The steps include treating the surface of a substrate loaded into a chamber with the thin film modification composition described in claim 1, The process involves injecting a precursor compound and a reaction gas into a chamber in this order, and forming a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and under a vacuum of less than 760 torr. Includes, A method for forming a thin film, characterized in that the reaction gas is an oxidizing agent or a reducing agent.

5. The steps include treating the surface of a substrate loaded into a chamber with the thin film modification composition described in claim 1, The steps include injecting an etching material into a chamber to form a vacuum-based etching film on a substrate, Includes, The etching substance is Cl ２ , CCl ４ , CF ２ Cl ２ , CF ３ Cl, CF ４ , CHF ３ , C ２ F ６ , SF ６ , BCl ３ , Br ２ , and one or more selected from CF ３ Br, a thin film forming method characterized by this.

6. The thin film formation method according to claim 4 or 5, characterized in that the chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

7. The thin film formation method according to claim 6, characterized in that the thin film modification composition and the precursor compound are transported into the chamber by a VFC (vapor flow control) method, a DLI (direct liquid injection) method, or an LDS (liquid delivery system) method, and the heating temperature of the injection line is 25 to 200°C on the substrate.

8. The etching material is Ar, H ２ , or O ２ The thin film formation method according to claim 5, characterized in that it is used in mixture with [another ingredient].

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