Thin film modifying composition, thin film forming method using the same, semiconductor substrate and semiconductor device manufactured by 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 method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. More specifically, the present invention relates to a thin film modification composition, which is composed of a film growth / film quality improving compound having a predetermined structure and a solvent having a specific dielectric constant, and which appropriately reduces the growth rate of a deposited film during a vacuum-based thin film process, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, improving the efficiency of an etching film, and significantly reducing impurity contamination, a method for forming a thin film using the same, and a semiconductor substrate manufactured thereby. [Background technology]

[0002] Increasing integration density of memory and non-memory semiconductor devices is leading to increasingly complex substrate topologies.

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

[0004] As a result, step coverage, which limits the thickness ratio of the deposition layer formed on the top and bottom of the microstructure in the depth direction, remains at a level of 90%, and the importance of this is increasing as it becomes increasingly difficult to express the electrical characteristics of the device. Since 100% step coverage means that the thickness of the deposition layer formed on the top and bottom of the microstructure is the same, it is necessary to develop technology that can achieve step coverage as close to 100% as possible.

[0005] The semiconductor thin film is made of a nitride film, a thin film, a metal film, etc. Examples of the nitride film include silicon nitride (SiN), titanium nitride (TiN), tantalum nitride (TaN), etc., examples of the thin film include silicon oxide (SiO2), hafnium oxide (HfO2), zirconium oxide (ZrO2), etc., and examples of the metal film include molybdenum film (Mo), tungsten (W), etc.

[0006] The thin film is generally used as a diffusion barrier between the silicon layer of a doped semiconductor and aluminum (Al), copper (Cu), etc., which are used as interlayer wiring materials, but is also used as an adhesion layer when a tungsten (W) thin film is deposited on a substrate.

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

[0008] When the deposition temperature is increased in order to achieve 100% step coverage, problems arise in terms of step coverage. First, in a deposition process that involves two types of material, a precursor and a reactant, an increase in deposition temperature not only leads to a steep increase in the growth rate of the thin film (GPC: Growth Per Cycle), but also, even if an ALD process is performed at 300°C in order to mitigate the increase in GPC caused by an increase in deposition temperature, the deposition temperature increases during the process, so it is difficult to say that this is a solution.

[0009] In addition, high-temperature processes are required to realize high-quality metal thin films in semiconductor devices. Research results have been reported showing that the concentration of carbon and hydrogen remaining in the thin film can be reduced by increasing the deposition temperature of the atomic layer to 400°C (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. First, in a deposition process consisting of two types of precursor and reactant, an increase in deposition temperature may lead to a steep increase in the growth rate of the thin film (GPC: Growth Per Cycle). In addition, even if a known shielding agent is used to mitigate the increase in GPC caused by an increase in deposition temperature, it has been confirmed that the GPC increases by about 10% at 300°C. In other words, when deposition is performed at 360°C or higher, it is difficult to expect the GPC reduction effect provided by the conventional known shielding agent.

[0011] Therefore, there is a demand for a thin film formation method that can effectively form thin films with complex structures even at high temperatures, has a low amount of residual impurities, and significantly improves film quality such as step coverage, thin film thickness uniformity, and electrical properties, as well as semiconductor substrates and the like manufactured thereby. Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above-mentioned problems of the prior art, and aims to provide a thin film modifying composition composed of a film growth / film quality improving compound having a predetermined structure and a solvent having a specified dielectric constant, which appropriately reduces the growth rate of a deposited film during a vacuum-based thin film process, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, improving the efficiency of an etching film, and remarkably reducing impurity contamination. The present invention also aims to provide a thin film modifying composition, a thin film forming method using the same, a semiconductor substrate manufactured thereby, and a semiconductor device including the same.

[0013] The present invention aims to improve the density and dielectric properties of thin films by improving the crystallinity and oxidation fraction of the thin films.

[0014] The above and other objects of the present invention can be achieved by the present invention described below. [Means for solving the problem]

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

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

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

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

[0019] When the thin film is a vapor-deposited film, the liquid halogen compound may contain compounds represented by the following chemical formulas 1-1 to 1-9.

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

[0021] [ka]

[0022] When the thin film is an etching film, the liquid halogen compound may contain compounds represented by the following chemical formulas 2-1 to 2-3.

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

[0024] [ka]

[0025] The liquid halogen compound can control the reaction aspect of the above-mentioned deposited or etched film.

[0026]

[0027] In the present invention, the liquid halogen compound may be used in combination with a non-polar solvent having a dielectric constant of 25 or less.

[0028] The dielectric constant is, for example, 25 or less, specifically 15 or less, preferably 10 or less. In this range, the dielectric constant does not show any reactivity with the liquid halogen compound, and therefore the effect to be provided by the liquid halogen compound can be maximized without adversely affecting the process.

[0029] The non-polar solvent having a dielectric constant of 25 or less may be, for example, a hydrocarbon-based solvent, a halogen-based solvent, a heterocycle-containing solvent, or an alcohol-based solvent.

[0030] The non-polar solvent having a dielectric constant of 25 or less may be at least one selected from the group consisting of octane, 1,2-dichloroethane, dimethylethylamine, tetrahydrofuran, N,N-dimethylformamide, isobutyl alcohol, and ethyl alcohol.

[0031]

[0032] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of:

[0033] Treating a surface of a substrate loaded in a chamber with the thin film modifying composition of claim 1;

[0034] Injecting a precursor compound and a reactant gas into a chamber in this order, and forming a vacuum-based deposition thin film on the substrate at 20 to 800°C and a vacuum of less than 760 torr;

[0035] The present invention provides a method for forming a thin film, wherein the reactive 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 precursor compounds can be delivered into the chamber by a Vapor Flow Control (VFC) method, a Direct Liquid Introduction (DLI) method, or a Liquid Delivery System (LDS) method.

[0038] At this time, the heating temperature of the deposition transfer line (hereinafter, referred to as the "injection line") may be within 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 reactive gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0041] The thin film may be a thin film having one or more layers of one or more metals 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 laminated thereon.

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

[0043]

[0044] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of:

[0045] injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate;

[0046] The etching material is at least one selected from the group consisting of Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

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

[0048] The thin film modifying composition and the precursor compound can be delivered into the chamber by a VFC method, a DLI method, or an LDS method.

[0049] The etching agent can be mixed with Ar, H2, or O2.

[0050]

[0051] A method for forming a thin film using the thin film modifying composition includes the steps of:

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

[0053] ii) a step of primarily purging the inside of the chamber with a purge gas.

[0054] The thin film modifying composition may be applied to a substrate loaded in a chamber under a temperature condition of 20 to 800°C.

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

[0056]

[0057] The thin film forming method includes:

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

[0059] ii) initially purging the interior of the chamber with a purge gas;

[0060] iii) vaporizing a precursor compound and adsorbing it in an area outside the modified area;

[0061] iv) second purging the interior of the chamber with a purge gas;

[0062] v) supplying a reaction gas into the chamber;

[0063] vi) a third step of purging the inside of the chamber with a purge gas.

[0064] The thin film modifying composition may be applied to a substrate loaded in a chamber under a temperature condition of 20 to 800°C.

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

[0066] The precursor compound may be 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 of more than 0.01 mTorr and not more than 100 torr.

[0067] The thin film modification composition, or precursor compound, may include a step of plasma post-treatment after being vaporized and injected.

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

[0069] The reaction gas is an oxidant or a reductant, and the reaction gas, the thin film modifying composition and the precursor compound can be delivered into the chamber by a VFC method, a DLI method or an LDS method.

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

[0071]

[0072] The present invention also provides a semiconductor substrate comprising a thin film produced by the above-mentioned thin film formation method.

[0073] The thin film may have a multi-layer structure of two or more layers.

[0074] The present invention further provides a semiconductor device including the semiconductor substrate described above.

[0075] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA), or 3D NAND flash memory. Effect of the Invention

[0076] According to the present invention, by using a thin film modifying composition composed of a film growth / film quality improving compound having a predetermined structure and a solvent having a specified dielectric constant in a vacuum-based thin film process, the growth rate of a deposited film in a vacuum-based thin film process can be appropriately reduced, and 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, and the etching efficiency can be improved. In addition, a thin film modifying composition can be provided that can significantly reduce impurity contamination.

[0077] In addition, the process by-products during the formation of the thin film are more effectively reduced, corrosion and deterioration are prevented, and the film quality is modified to improve the crystallinity of the thin film, thereby improving the electrical characteristics of the thin film.

[0078] Furthermore, when forming a thin film, the process by-products are reduced, the reaction rate is lowered, and the thin film growth rate is appropriately reduced, so that even when a thin film is formed on a substrate having a complex structure, the step coverage and thin film density can be improved, and further, a thin film formation method using this and a semiconductor substrate manufactured thereby can be provided. [Brief description of the drawings]

[0079] [Figure 1] FIG. 1 is a graph showing 1H-NMR measurements to confirm the reactivity during synthesis and deposition of thin film modification compositions, showing a thin film obtained using 2-chloro-2-methylbutane alone (top) and a thin film obtained using a 1:1 molar ratio blend of 2-chloro-2-methylbutane and octane (bottom). [Diagram 2] FIG. 1H-NMR was measured to confirm the reactivity during synthesis and deposition of the thin film modification composition, showing a thin film obtained using iodocyclopentane alone (top) and a thin film obtained using a 1:1 molar ratio blend of iodocyclopentane and 1,2-dichloroethane (bottom). [Diagram 3] Graph showing 1H-NMR measurements to confirm the reactivity during synthesis and deposition of thin film modification compositions, showing a thin film obtained using 1-chloro-1-methylcyclohexane alone (top) and a thin film obtained using a 1:1 molar ratio blend of 1-chloro-1-methylcyclohexane and octane (bottom). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0080] The thin film modifying composition described above, the thin film forming method using the same, and the semiconductor substrate produced thereby will be described in detail below.

[0081] In this description, the term "thin film modification" means, unless otherwise specified, controlling the surface of a substrate that is used as a surface chemically reactive surface in a deposition process.

[0082] In this description, unless otherwise specified, the term "improving film growth / film quality" means not only reducing, preventing or blocking the adsorption of a precursor compound for forming a thin film onto a substrate, but also reducing, preventing or blocking the adsorption of process by-products onto a substrate to improve film growth, or improving film quality such as electrical properties and thin film density.

[0083] In this description, the dielectric constant can be determined using a value known in the art (calculated value at 20° C.). https: / / macro.lsu.edu / howto / solvents / Dielectric%20Constant%20.htm reference).

[0084] The present inventors have found that by using a film growth / film quality improving compound of a specific structure and a solvent with a specific dielectric constant as a thin film modifying composition for modifying the surface of a substrate and improving the deposition or etching process in a vacuum-based deposition or etching process, the growth rate of the deposited film can be appropriately reduced, and 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 efficiency of the etching film can be improved, and in particular, it is possible to deposit the thin film at a thin thickness, and the amount of O, Si, metal, metal oxide, and even the amount of carbon remaining as process by-products, which was difficult to reduce in the past, can be improved. Based on this finding, the present invention has been completed by incorporating the findings into research on film growth / film quality improving compounds.

[0085]

[0086] The thin film modifying composition of the present invention can be applied to a vacuum-based deposition film or a vacuum-based etching film.

[0087] The deposited or etched film may be provided 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, for example, and may provide a modified region for an oxide film, a nitride film, a metal film, or a selective thin film thereof. In this case, the effect to be achieved in the present invention may be sufficiently obtained.

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

[0089] The thin film can be used in semiconductor devices not only as a commonly used diffusion barrier film, but also as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a blocking thin film, or a charge trap.

[0090]

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

[0092] [Chemical formula 3]

[0093] [ka]

[0094] (In the above formula 3, M is at least one 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, where -X is F, Cl, Br, or I, and -R is C1-C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed into 2 to 6 depending on the oxidation value 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 a ligand, and if 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 L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

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

[0097] Said L 1 , L 2 , L 3 and L 4 is -R, -X or Cp, which may be the same or different, where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may have a linear or cyclic structure.

[0098] In addition, the above-mentioned L 1 , L 2 , L 3 and L 4 -NR 2 or Cp, which may be the same or different, where -R is H, C1-C10 alkyl, C1-C 10 Alkenes, C1-C 10 alkane, iPr, or tBu.

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

[0100] Specifically, examples of aluminum precursor compounds that can be used include Al(CH3)3 and AlCl4.

[0101] Examples of hafnium precursor compounds that can be used include tris(dimethylamido)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 modifying composition of the present invention can control the surface of the substrate to which the precursor compound is to be adsorbed in advance, thereby reducing the rate at which the precursor compound is adsorbed onto the substrate, thereby controlling the growth of a vacuum-based thin film and controlling the film quality.

[0105] The thin film modifying composition may include a liquid halogen compound having a vapor pressure of 1 torr (25°C) or more and a non-polar solvent having a dielectric constant of 25 or less. In this case, when forming a deposition film or an etching film, it has the effect of suppressing side reactions, controlling the thin film growth rate, reducing process by-products in the thin film, reducing corrosion and deterioration, improving the crystallinity of the thin film, and significantly improving step coverage and thin film thickness uniformity while minimizing impurity contamination, even when a thin film is formed on a substrate having a complex structure.

[0106] As a specific example, the refractive index of the halogen compound may be within 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 large, the step coverage is excellent, and the effect of improving the thin film density and the electrical properties of the thin film are further excellent.

[0107] The liquid halogen compound is preferably used in an atomic layer deposition (ALD) process, and in this case, has the advantages of effectively protecting the surface of the substrate and effectively removing process by-products while not interfering with the adsorption of precursor compounds or etching by etching substances.

[0108] The liquid halogen compound is preferably liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20°C) may be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, the modified region is effectively formed, and there is an effect that the step coverage, the film thickness uniformity of the thin film, and the improvement of the film quality are excellent.

[0109] More preferably, the liquid halogen compound has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.3g / cm 3 The vapor pressure (20° C.) can be 1 to 260 mmHg. Within this range, the modified region is effectively formed, and there is an effect that the step coverage, the thin film thickness uniformity, and the improvement of the film quality are excellent.

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

[0111]

[0112] The liquid halogen compound contains an alkyl halide having 1 to 10 carbon atoms, and thus has a large effect of reducing process by-products, excellent step coverage, and is further effective in improving the thin film density and electrical properties of the thin film.

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

[0114]

[0115] When the thin film is a deposition film, the liquid halogen compound may be at least one selected from the compounds represented by the following chemical formulas 1-1 to 1-9. In this case, when forming a deposition film, a relatively rough thin film is formed, side reactions are suppressed, the thin film growth rate is controlled, process by-products in the thin film are reduced, corrosion and deterioration are reduced, and the crystallinity of the thin film is improved. Even when a thin film is formed on a substrate having a complex structure, not only can the step coverage and the thickness uniformity of the thin film be significantly improved, but also contamination by impurities can be minimized.

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

[0117] [ka]

[0118] When the thin film is an etching film, the liquid halogen compound may be preferably a compound represented by the following chemical formulas 2-1 to 2-3. In this 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] The above-mentioned liquid halogen compound can be used alone, but considering the severe atmosphere under a vacuum base, it is preferable to use it in combination with a specific organic solvent, since this makes it possible to carry out the process more efficiently.

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

[0124] Examples of the non-polar solvent having a dielectric constant of 25 or less include hydrocarbon solvents, halogen-based solvents (excluding the above-mentioned liquid halogen compounds), heterocycle-containing solvents, and alcohol-based solvents.

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

[0126] The halogen-based solvent may be a linear hydrocarbon compound substituted with a terminal halogen, in which at least one halogen is substituted, preferably two or more halogens, and for example, 1,2-dichloroethane (d: 10.7 at 25°C) can be used.

[0127] The heterocycle-containing solvent may contain nitrogen or oxygen.

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

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

[0130] Examples of the alcohol-based solvent 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 modifying composition may include at least one compound selected from the compounds represented by the above formulas 1-1 to 1-9 and a non-polar solvent having a dielectric constant of 25 or less. In this case, the composition has a large effect of controlling the growth rate of the deposition film, a large effect of removing process by-products, and an excellent effect of improving step coverage and film quality. Even if applied to a substrate with a complex structure, the composition ensures the uniformity of the thin film and significantly improves step coverage. In particular, the composition can be deposited on a thin thin film, and can provide an effect of improving O, Si, metal, metal oxide, and even carbon residues that were difficult to reduce in the past, which can be provided even when an etched film is manufactured.

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

[0134] The thin film may be a thin film having one or more layers of one or more metals 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 laminated thereon.

[0135] The thin film modifying composition may provide a modified region for a thin film.

[0136] The thin film modifying composition is characterized in that it does not remain on the thin film.

[0137] In this case, unless otherwise specified, "not remaining" refers to the presence of C element less than 0.1 atomic % (atom%), Si element less than 0.1 atomic % (atom%), N element less than 0.1 atomic % (atom%), and halogen element less than 0.1 atomic % (atom%) when analyzing the components by XPS. More preferably, in a measurement method using secondary ion mass spectrometry (SIMS) in which measurements are made while digging into the substrate in the depth direction, or a measurement method using X-ray photoelectron spectroscopy (XPS), when considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using the thin film modifying composition under the same deposition conditions, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0138] As an example, the thin film may contain halogen compounds at 100 ppm or less.

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

[0140] The liquid halogen compound, organic solvent and precursor compound may preferably be a compound having a purity of 99.9% or more, a compound having a purity of 99.95% or more, or a compound having a purity of 99.99% or more. For reference, when a compound having a purity of less than 99% is used, there is a risk that impurities may remain in the thin film or cause a side reaction with the precursor or reactant, so it is preferable to use a substance having a purity of 99% or more as much as possible.

[0141]

[0142] The method for forming a thin film of the present invention includes the steps of treating a surface of a substrate loaded into a chamber with the above-mentioned thin film modifying composition, and injecting a precursor compound and a reactive gas into the chamber in this order to form a vacuum-based deposited thin film on the substrate at 20 to 800°C and a vacuum of less than 760 torr, wherein the reactive 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 reduced, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, while minimizing impurity contamination.

[0143] In the step of treating with the thin film modifying composition, the feeding time (seconds (sec)) of the thin film modifying composition to the surface of the substrate is preferably 0.01 to 10 seconds per cycle, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 5 seconds. Within this range, there are advantages such as a low thin film growth rate, excellent step coverage and economy, and the ability to minimize impurity contamination.

[0144] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle in a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle in 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 thin film modification composition to form a modified region on the surface of a substrate loaded into a chamber, and ii) first purging the inside of the chamber with a purge gas.

[0147] As a preferred embodiment, the thin film modification method and further the thin film formation method may include the steps of: i) vaporizing the thin film modification composition and applying it to a surface of a substrate loaded into a chamber; ii) primarily purging the interior of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it onto the surface of the substrate loaded into the chamber; iv) secondly purging the interior of the chamber with a purge gas; v) supplying a reaction gas into the chamber; and vi) thirdly purging the interior of the chamber with a purge gas.

[0148] In this case, steps i) to vi) are regarded as a unit cycle, and the cycle can be repeated until a thin film having a desired thickness is obtained. In this manner, when the thin film modifying composition of the present invention is added prior to the precursor compound in one cycle and adsorbed onto the substrate, even if deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, the process by-products generated are effectively removed, the resistivity of the thin film is reduced, and the step coverage is significantly improved.

[0149] In another preferred embodiment, the substrate may be prepared by applying the thin film modifying composition to a substrate loaded in a chamber under a temperature condition of 20 to 800°C.

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

[0151]

[0152] In the thin film forming method, for example, when the thin film modifying composition is deposited before or after deposition of the precursor compound, a unit cycle can be repeated 1 to 99,999 times as necessary, and preferably a unit cycle can be repeated 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 effect to be achieved in the present invention can be sufficiently obtained while obtaining the desired thin film thickness.

[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 in the case of a precursor having a vapor pressure of 1 mTorr to 100 torr at 25°C, the effect of forming a modified region by the thin film modifying composition can be maximized despite natural oxidation.

[0155] In the present invention, the chamber may be, for example, 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, after the liquid halogen compound or precursor compound is vaporized and injected, a step of plasma post-treatment may be included, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0158]

[0159] In the case where the thin film modifying composition is first adsorbed on the substrate, the precursor compound is then adsorbed, and then the precursor compound is adsorbed, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed thin film modifying agent or thin film modifying composition is not particularly limited as long as it is an amount sufficient to remove the unadsorbed thin film modifying composition, but as an example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed thin film modifying composition can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of the purge gas and thin film modifying composition introduced are each based on one cycle, and the volume of the thin film modifying composition means the volume of the vaporized thin film modifying composition, or the volume of the vaporized liquid halogen compound and non-polar solvent, respectively.

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

[0161]

[0162] In addition, 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 an amount sufficient to remove the unadsorbed precursor compound, but as an example, it may be 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times based on the volume of the precursor compound introduced into the chamber, and 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 the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound means the volume of the vaporized precursor compound vapor.

[0163]

[0164] Furthermore, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the chamber may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times the volume of the reaction gas introduced into the chamber, and within this range, the desired effect can be sufficiently obtained. Here, the amounts of the purge gas and reaction gas introduced are each based on one cycle.

[0165]

[0166] The thin film modifying composition and the precursor compound can be preferably delivered into the chamber by the VFC method, the DLI method or the LDS method, and more preferably, are delivered into the chamber by the LDS method.

[0167] The liquid halogen compound and the non-polar solvent constituting the thin film modifying composition may be transported into the chamber separately, or may be transported together in a mixed state.

[0168] The substrate loaded in the chamber may be heated to, for example, 100 to 650°C, specifically, 150 to 550°C, and the thin film modifying composition or precursor compound may be injected onto the substrate in an unheated or heated state, and the heating conditions may be adjusted during the deposition process after being injected unheated depending on deposition efficiency. For example, the thin film modifying composition or precursor compound may be injected onto the substrate at 100 to 650°C for 1 to 20 seconds.

[0169]

[0170] The ratio of the precursor compound and the thin film modifying composition fed into the chamber (mg / cycle) may be 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 the effect of reducing process by-products are large.

[0171]

[0172] For example, when the thin film forming method uses the thin film modifying 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, a relatively rough thin film is formed using the film growth / film quality improving compound or thin film modifying composition having the above structure, and the growth rate of the formed thin film is significantly reduced. Even if the method is applied to a substrate having a complex structure under high temperature, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, it is possible to provide an effect that a thin thin film can be deposited, and O, Si, metal, metal oxide, and even carbon residues that were previously difficult to reduce as process by-products are improved.

[0173] [Formula 1]

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

[0175] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding the thin film modifying composition. DR f (Final Deposition Rate) is the deposition rate of the thin film formed by adding the thin film modifying composition when the above-mentioned process is carried out. Here, the deposition rate (DR) is a value measured by an ellipsometer device under conditions of room temperature and normal pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0176] In Equation 1, the thin film growth rate per cycle when the thin film modifying composition is used and when it is not used means the deposition thickness (Å / cycle) of the thin film per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by dividing the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure by the total number of cycles to obtain an average deposition rate.

[0177] In the above formula 1, "when no thin film modifying composition was used" refers to a case where a thin film is manufactured by adsorbing only a precursor compound onto a substrate during a thin film deposition process, and specifically refers to a case where a thin film is formed by omitting the step of adsorbing a thin film modifying composition and the step of purging unadsorbed thin film modifying composition from the above thin film formation method.

[0178]

[0179] In the thin film formation method, the strength (c / s) of residual halogen in the thin film based on a thin film thickness of 100 (Å / cycle), measured based on SIMS, can 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 can be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within such a range, the effect of preventing corrosion and deterioration is outstanding.

[0180] In this description, the purge rate 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 or approximately as an atomic mono-layer, which is advantageous in terms of film quality.

[0181]

[0182] The ALD (atomic layer deposition) process is very advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and has advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin film growth mechanism.

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

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

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

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

[0187] The present invention may also include a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, the thin film manufacturing apparatus including 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 the thin film precursor, and a second transport means for transporting the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and the transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the technical field to which the present invention pertains.

[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, there can be provided a method for forming a thin film, comprising the steps of treating a surface of a substrate loaded into a chamber with the above-mentioned thin film modifying composition, and injecting an etching material into the chamber to form a vacuum-based etching film on the substrate, wherein the etching material is one or more selected from the group consisting of Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0191] The etching material may be a mixture of Ar, H2, or O2, and other than this, details that overlap with the formation of the deposition film will be 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 above. In such a case, the thin film has excellent step coverage and thickness uniformity, and has excellent density and electrical properties.

[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. Within this range, the thin film has 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, there is an effect that the thin film growth rate is reduced while the thin film properties are excellent.

[0196] As an example, the thin film has a step coverage 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 on a substrate, and has the advantage that it can be applied to next-generation semiconductor devices.

[0197] The thin film thus produced preferably has a thickness of 20 nm or less, a dielectric constant of 5 to 29 based on a thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage rate of 90% or more. Within these ranges, the thin film has the effect of having excellent performance as a dielectric film or a blocking film, but is not limited thereto.

[0198]

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

[0200] The underlayer film may, for example, comprise one or more 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 intermediate layer is, for example, Ti xN y , preferably TN.

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

[0203] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA), or 3D NAND flash memory.

[0204]

[0205] Below, preferred embodiments and drawings are presented to deepen understanding of the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the technical spirit thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0206]

[0207] [Example]

[0208] <Test Example 1>

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

[0210] For the experiment, among the solvents having a dielectric constant value of 15 or less, the compound represented by the following chemical formula 4-1 (d at 25°C: 1.9), the compound represented by the following chemical formula 4-2 (d at 25°C: 3.2), the compound represented by the following chemical formula 4-3 (d at 25°C: 7.6), the compound represented by the following chemical formula 4-4 (d at 25°C: 10.7), the compound represented by the following chemical formula 4-5 (d at 25°C: 16.7), the compound represented by the following chemical formula 4-6 (d at 25°C: 24.6), and the compound represented by the following chemical formula 4-7 (d at 25°C: 36.7) were mixed with the compounds represented by the above-mentioned chemical formulas 1-1, 1-4, and 1-7 in a 1:1 molar ratio, 1 The degree of reactivity was confirmed by the presence or absence of new impurity peaks using H-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. Here, when a new impurity peak is observed, it is considered that there is reactivity and is indicated by O, and when no new impurity peak is observed, it is considered that there is no reactivity 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 in which compounds represented by Chemical Formula 4-1, Chemical Formula 4-2, Chemical Formula 4-3, and Chemical Formula 4-4, each having a dielectric constant of 15 or less, were blended, no reactivity was observed regardless of the type of liquid halogen compound, and this was found to be effective in improving the deposition process. On the other hand, in Reference Example 1 in which a compound represented by Chemical Formula 4-5, each having a dielectric constant slightly exceeding 15, was blended, this was found to be effective in improving the deposition process depending on the type of liquid halogen compound, and this was found to be effective in improving the deposition process depending on the type of liquid halogen compound.

[0234] On the other hand, Reference Example 2, which contains a compound represented by formula 4-6 having a dielectric constant slightly exceeding 15, was also observed to have no reactivity with iodocyclopentane, and is therefore considered to be suitable for improving the deposition process depending on the type of liquid halogen compound.

[0235] In contrast, in the case of Comparative Example 1, in which the compound represented by Chemical Formula 4-7, which has a dielectric constant far exceeding 25, was blended, it was observed that the compound had reactivity regardless of the type of liquid halogen compound, and was therefore not suitable for improving the deposition process.

[0236]

[0237] <Test Example 2>

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

[0239] Specifically, in Table 1 below, for the deposition of SiN in Comparative Example 1-1, hexachlorodisilane (HCDS) precursor is utilized, the canister heating temperature is 35°C, the N2 carrier gas flow rate is 40sccm injected for 3 seconds, the NH3 flow rate is 1000sccm injected for 30 seconds, and the N2 purge gas flow rate is 1000sccm injected for 12 seconds, and 100 to 150 cycles are repeated.

[0240] At this time, the conditions were maintained: the heating temperature of the canister was 50°C, and the flow rate of N2 carrier gas was 100sccm for 3 seconds. In addition, 100 to 150 cycles were repeated using the process of separately injecting the substances represented by the above-mentioned chemical formulas 1-1, 1-4, and 1-7 for 3 seconds each.

[0241] Specifically, the materials represented by Chemical Formula 1-1, Chemical Formula 1-4, and Chemical Formula 1-7 were mixed with organic solvents represented by Chemical Formulas 4-1 to 4-6 below, respectively, in a 1:1 molar ratio according to the compositions shown in Table 1, and used as a liquid delivery system (LDS).

[0242] For the thin films obtained in Examples 1 to 4, Comparative Example 1, and Reference Examples 1 and 2, the thickness of the 10 nm SiN thin film was analyzed by carrying out ellipsometry optical analysis.

[0243] In addition, for the thin films obtained in Examples 1 to 4, Comparative Example 1, and Reference Examples 1 and 2, the SiN thin film formed to a thickness of 10 nm was subjected to ellipsometry optical analysis fitting to measure the thickness, and the obtained thickness was divided by the total ALD cycle to measure the deposition rate of the film thickness per cycle (Å / 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, it was confirmed that the deposition rate was reduced by 20% or more in Reference Examples 1 and 2 only when the compound represented by Chemical Formula 1-7 was used.

Claims

1. a liquid halogen compound having a vapor pressure of 1 torr (25° C.) or more; a non-polar solvent having a dielectric constant of 25 or less; A thin film modifying composition comprising:

2. The thin film modifying composition according to claim 1, wherein the liquid halogen compound is an alkyl halide having 1 to 10 carbon atoms.

3. The thin film modifying composition according to claim 1, wherein the liquid halogen compound has a refractive index of 1.40 to 1.

60.

4. The liquid halogen compound includes compounds represented by the following chemical formulas 1-1 to 1-9 when the thin film is a deposition film, and includes compounds represented by the following chemical formulas 2-1 to 2-3 when the thin film is an etching film. The thin film modifying composition according to claim 1. [Chemical formulas 1-1 to 1-9] 【Chemistry 1】 [Chemical formulas 2-1 to 2-3] 【Chemistry 2】

5. The vacuum-based thin film modifying composition according to claim 1, wherein the non-polar solvent having a dielectric constant of 25 or less is a hydrocarbon-based solvent, a halogen-based solvent, a heterocycle-containing solvent, or an alcohol-based solvent.

6. The non-polar solvent having a dielectric constant of 25 or less is at least one selected from the group consisting of octane, 1,2-dichloroethane, dimethylethylamine, tetrahydrofuran, N,N-dimethylformamide, isobutyl alcohol, and ethyl alcohol.

7. Treating a surface of a substrate loaded in a chamber with the thin film modifying composition of claim 1; Injecting a precursor compound and a reactant gas into a chamber in this order to form a vacuum-based deposition thin film on the substrate under conditions of 20-800° C. and a vacuum of less than 760 torr; Including, The thin film forming method, wherein the reactive gas is an oxidizing agent or a reducing agent.

8. Treating a surface of a substrate loaded in a chamber with the thin film modifying composition of claim 1; injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate; Including, The etching material is Cl ２ , CCl ４ , C.F. ２ C ２ , C.F. ３ Cl, CF ４ , C.H.F. ３ , C ２ F ６ , S.F. ６ , BCl ３ , B ２ , and C.F. ３ Br.

9. 9. The method of claim 7 or 8, wherein 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.

10. The method of claim 9, wherein the thin film modifying composition and precursor compound are delivered into the chamber by a vapor flow control (VFC), direct liquid introduction (DLI) or liquid delivery system (LDS), and the heating temperature of the injection line is 25 to 200° C. on the substrate.

11. The etching material is Ar, H ２ , or O ２ 9. The method for forming a thin film according to claim 8, wherein the above is used in combination with a solvent.

12. A semiconductor substrate comprising a thin film produced by the thin film formation method according to claim 7 or 8.

13. 13. The semiconductor substrate according to claim 12, wherein the thin film has a multi-layer structure of two or more layers.

14. A semiconductor device comprising the semiconductor substrate of claim 12.

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