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 modifying composition, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. The present invention has the effect of improving the reaction rate by using a step coverage improving agent and an amine compound in combination, appropriately lowering the thin film growth rate, and significantly improving the step coverage and the film thickness uniformity of the thin film even when the thin film is formed under high temperature conditions on a substrate having a complex structure, and reducing impurities to improve the film quality.

Description

[Technical field]

[0001] The present invention relates to a thin film modifying 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 modifying composition comprising a step coverage improving agent and an amine compound, which forms a deposition layer of uniform thickness on a substrate as a shielding region due to the difference in the adsorption distribution degree of the compound, thereby reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate, thereby significantly improving step coverage and uniformity of the thin film thickness even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurities, a thin film forming method using the same, and a semiconductor substrate manufactured thereby. [Background technology]

[0002] As memory and non-memory semiconductor devices continue to increase in integration density, substrate topologies are becoming increasingly complex.

[0003] For example, the ratio of the width to the depth of a microstructure (hereinafter also referred to as the "aspect ratio") is increasing to 20:1 or more, and even 100:1 or more. The larger the aspect ratio, 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] That is, in order for the thin film deposited on the substrate to have excellent uniform physical properties, it is essential that the thin film has high step coverage. Although the atomic layer deposition (ALD) process, which utilizes surface reactions, is used rather than the chemical vapor deposition (CVD) process, which mainly utilizes gas phase reactions, there are still problems in achieving 100% step coverage.

[0006] It is difficult to increase the deposition temperature to achieve 100% step coverage. First, in a deposition process consisting of two parts, a precursor and a reactant, an increase in deposition temperature leads to a rapid increase in the growth rate of thin films (GPC). Even if the ALD process is performed at 300°C to mitigate the increase in GPC caused by an increase in deposition temperature, the deposition temperature increases during the process, so this is not a solution.

[0007] In addition, high-temperature processes are necessary to realize high-quality metal oxide films for semiconductor devices. Research has shown that increasing the atomic layer deposition temperature to 400°C reduces the concentration of residual carbon and hydrogen in the thin film (see J.Vac.Sci.Technol.A, 35(2017)01B130).

[0008] However, the higher the deposition temperature, the more difficult it becomes to ensure the step coverage. First, in a deposition process consisting of two parts, a precursor and a reactant, an increase in deposition temperature may cause a rapid increase in GPC (thin film growth rate). In addition, even if a known step coverage improver is applied 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 a GPC reduction effect from a conventionally known step coverage improver.

[0009] Therefore, there is a need for a thin film formation method that can effectively form thin films having complex structures even at high temperatures, with a small amount of residual impurities, and significantly improve step coverage and thin film thickness uniformity, as well as semiconductor substrates and the like manufactured thereby. Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made to solve the problems of the prior art described above, and aims to provide a thin film modifying composition that effectively shields a substrate by using a step coverage improving agent in combination with an amine compound to improve the reaction rate and appropriately reduce the thin film growth rate, 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 reducing impurities and improving film quality, a thin film formation method using the same, and a semiconductor substrate manufactured thereby.

[0011] 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.

[0012] The above and other objects of the present invention can be achieved by the present invention described below. [Means for solving the problem]

[0013] In order to achieve the above object, the present invention provides a thin film modifying composition comprising 50 to 99 parts by weight of a step coverage improving agent containing a compound represented by the following chemical formula 1 and 1 to 50 parts by weight of an amine compound, wherein the amine compound is at least one selected from the group consisting of alkylamines having a boiling point in the range of 5 to 200°C and arylamines having a boiling point in the range of 50 to 260°C.

[0014] chemical formula 1

[0015] [ka]

[0016] (In the above Chemical Formula 1, R 1 and R 2 are each independently H or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 4.

[0017] The step coverage improving agent may contain a linear or cyclic, saturated or unsaturated hydrocarbon having two or more oxygen (O), phosphorus (P) or sulfur (S) atoms and having 3 to 15 carbon atoms.

[0018] The step coverage improving agent may include a compound having a structure containing oxygen (O), phosphorus (P), or sulfur (S) at both ends of a central carbon atom connected to oxygen by a double bond.

[0019] The step coverage improving agent may include a compound having a structure including oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to oxygen by a double bond and carbon (C) at the other end.

[0020] The step coverage improving agent may include one or more compounds selected from the compounds represented by the following Chemical Formulas 1-1 to 1-7.

[0021] Chemical formula 1-1~1-7

[0022] [ka]

[0023] The step coverage improving agent may have a refractive index (measured at 20 to 25° C.) of 1.30 or more, 1.3 to 1.5, 1.35 to 1.48, or 1.36 to 1.46.

[0024]

[0025] The boiling point of the amine compound may be within the range of 5 to 200°C, specifically 50 to 150°C, and preferably 100 to 140°C.

[0026] The amine compound may preferably be a liquid type at room temperature in order to improve the spreadability and uniformity of the step coverage improving agent.

[0027] The amine compound may be a compound represented by the following Formula 3:

[0028] chemical formula 3

[0029] [ka]

[0030] (In the above Chemical Formula 3, R3, R4, and R5 are each independently selected from H, an alkane having 1 to 5 carbon atoms, an alkene having 1 to 5 carbon atoms, an alkane having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms, and two or more of R3, R4, and R5 may be bonded to each other to form a cyclic structure.)

[0031] The alkylamine may be one or more selected from the compounds represented by the following formulas 3-1 to 3-5.

[0032] Chemical formula 3-1~3-5

[0033] [ka]

[0034] The arylamine may be at least one selected from the compounds represented by the following formulas 4-1 to 4-9.

[0035] Chemical formula 4-1~4-9

[0036] [ka]

[0037] The amine compound may have a refractive index of 1.30 or more, 1.3 to 1.7, 1.35 to 1.7, or 1.36 to 1.69.

[0038]

[0039] The thin film modifying composition may have a deposition rate reduction rate, represented by the following Equation 1, of 5% or more.

[0040] Formula 1

[0041]

number

[0042] (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 the unit is Å / cycle.)

[0043] The thin film can improve the step coverage during the formation of a laminated film 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.

[0044] 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 block oxide film, or a charge trap, and can improve the step coverage during the formation process.

[0045]

[0046] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of:

[0047] The method includes the step of injecting a thin film modifying composition containing 50 to 99 parts by weight of a step coverage improving agent containing the compound represented by Chemical Formula 1 and 1 to 50 parts by weight of an amine compound into a chamber to shield a surface of a loaded substrate, the amine compound being at least one selected from the group consisting of alkylamines having a boiling point in the range of 5 to 200°C and arylamines having a boiling point in the range of 50 to 260°C.

[0048] The precursor compound used in the thin film formation method may be a compound represented by the following Chemical Formula 2.

[0049] chemical formula 2

[0050] [ka]

[0051] (In the above formula 2, 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 are -H, -X, -R, -OR, -NR or Cp (cyclopentadiene)2, which may be the same or different from each other, where -X is F, Cl, Br or I, and -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed from 2 to 6 depending on the oxidation value of the central metal (M).

[0052] 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.

[0053]

[0054] In the above Chemical Formula 2, L 1 , L 2 , L 3 and L 4 is -H, -X or -R, which may be the same or different, and where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may be linear or cyclic.

[0055] In the above Chemical Formula 2, L 1 , L 2 , L 3 and L 4 is -H, -OR, -NR or Cp (cyclopentadiene)2, which may be the same or different, where -R is H, C1 to C 10 Alkyl, C1-C 10 Alkenes, C1-C 10 alkane, iPr, or TBu.

[0056] In the above Chemical Formula 2, 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.

[0057]

[0058] The present invention also relates to

[0059] i) vaporizing said thin film modifying composition to mask the surface of the substrate loaded in the chamber;

[0060] ii) initially purging the interior of the chamber with a purge gas;

[0061] iii) vaporizing a precursor compound and allowing it to adsorb in an area outside the shielded area;

[0062] iv) second purging the interior of the chamber with a purge gas;

[0063] v) supplying a reaction gas into the chamber;

[0064] vi) a third step of purging the inside of the chamber with a purge gas.

[0065] The precursor compound may be a precursor that is a molecule consisting of one or more species 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 has a vapor pressure at 25°C of more than 0.01 mTorr and not more than 100 Torr.

[0066] 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.

[0067] After the thin film modification composition or precursor compound has been vaporized and injected, a plasma post-treatment step may be included.

[0068] The amount of the purge gas introduced into the chamber in each of the steps i) and iv) may be 10 to 100,000 times the volume of the introduced thin film modifying composition.

[0069] The reactive gas may be an oxidizing agent, a nitriding agent or a reducing agent, and the reactive gas, the thin film modification composition and the precursor compound may 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.

[0070] The thin film may be a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0071] The substrate loaded into the chamber is 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.

[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 also 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, it is possible to provide a thin film modifying composition that effectively blocks adsorption to the substrate surface, improves the reaction rate, and appropriately reduces the thin film growth rate, thereby improving step coverage even when a thin film is formed under high temperature conditions on a substrate having a complex structure.

[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] In addition, the process by-products can be reduced during thin film formation, and step coverage and thin film density can be improved. Furthermore, a thin film formation method using the same and a semiconductor substrate manufactured thereby can be provided. [Brief description of the drawings]

[0079] [Figure 1] FIG. 2 is a diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0080] [Diagram 2] FIG. 2 is a graph showing a comparison of the calculated non-uniformity for each of the thin films obtained in Examples 1 and 2 and Comparative Examples 2 and 3 described below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0081] 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.

[0082] In this description, unless otherwise specified, the term "step coverage improving agent" 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, thereby improving step coverage.

[0083] In this description, the term "shielding" means, unless otherwise specified, not only reducing, preventing or blocking precursor compounds for forming a thin film from adsorbing onto a substrate, but also reducing, preventing or blocking process by-products from adsorbing onto a substrate.

[0084]

[0085] The present inventors have found that, in order to form a thin film on the surface of a substrate loaded inside a chamber, a step coverage improving agent capable of blocking the adsorption of a precursor compound to be supplied and an amine compound capable of modifying the uniformity of the thin film formed can be used in combination to improve the reaction rate under high temperature conditions, and even if applied to a substrate with a complex structure, the film quality can be improved to ensure the uniformity of the thin film, thereby significantly improving the step coverage, and in particular, it is possible to deposit a thin film, and it is possible to improve O, Si, metal, metal oxide, and even the amount of carbon remaining, which was difficult to reduce in the past, that remain as process by-products. Based on this finding, the present invention has been completed by incorporating it into research on a thin film modifying composition.

[0086]

[0087] The thin film may be provided as one or more precursors selected from the group consisting of, for example, 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 provide an oxide film, a nitride film, or a metal film. In this case, the effects to be achieved in the present invention may be sufficiently obtained.

[0088] Specific examples of the thin film include a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, and an aluminum oxide film.

[0089] The thin film means that the film composition also contains SiH and SiOH.

[0090] The thin film can be used 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 block oxide film, or a charge trap, and can be used in semiconductor devices by improving the step coverage during the formation process.

[0091]

[0092] The precursor compound used in the present invention to form a thin film may be 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 having a vapor pressure of 1 mTorr to 100 Torr at 25° C.

[0093] As an example of the precursor compound, a compound represented by the following Chemical Formula 2 can be used.

[0094] chemical formula 2

[0095] [ka]

[0096] (In the above formula 2, 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 are -H, -X, -R, -OR, -NR or 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 to 2 to 6 depending on the oxidation value of the central metal.)

[0097] 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.

[0098] 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 such as a large effect of reducing process by-products and excellent step coverage, as well as an effect of improving thin film density and further excellent electrical properties, insulating properties and dielectric properties of the thin film.

[0099] Said L 1 , L 2 , L 3 and L 4 is -H, -X, or -R, which may be the same or different, and where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may have a linear or cyclic structure.

[0100] In addition, the above-mentioned L 1 , L 2 , L 3 and L 4 is -H, -OR, -NR or Cp (cyclopentadiene)2, which may be the same or different, where -R is H, C1 to C 10 Alkyl, C1-C 10 Alkenes, C1-C 10 alkane, iPr, or tBu.

[0101] In addition, in the above-mentioned Chemical Formula 2, 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.

[0102] Specifically, examples of silicon precursor compounds include SiH4, SiHCl3, SiH2Cl2, SiCl4, Si2Cl6, Si3Cl8, and Si4Cl. 10 , SiH2[NH(C4H9)]2, Si2(NHC2H5)4, Si3NH4(CH3)3, and one or more selected from SiH3[N(CH3)2], SiH2[N(CH3)2]2, SiH[N(CH3)2]3, and Si[N(CH3)2]4 can be used.

[0103] 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.

[0104] As the aluminum precursor compound, for example, trimethyl aluminum (TMA), tris(dimethylamido)aluminum (TDMAA), aluminum trichloride (AlCl3) can be used.

[0105]

[0106] The thin film modifying composition may be composed of a step coverage improving agent and an amine compound.

[0107] Here, the step coverage improving agent is characterized by containing a compound having one or more unshared electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P), preferably two or more oxygen (O), phosphorus (P) or sulfur (S), and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms. In this case, when forming a thin film, a shielding region that does not remain in the thin film is formed to form a relatively sparse thin film, 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, the crystallinity of the thin film is improved, a stoichiometric oxidation state is reached when a metal oxide film is formed, and even when a thin film is formed on a substrate having a complex structure under high temperature conditions, there are effects of significantly improving step coverage and thin film thickness uniformity.

[0108] As a specific example, the step coverage improver includes a compound having a structure containing oxygen (O), phosphorus (P) or sulfur (S) at both ends of a central carbon atom connected to oxygen by a double bond, and thus has a large effect of reducing process by-products and excellent step coverage, as well as an effect of improving thin film density and excellent electrical properties of the thin film.

[0109] The step coverage improver may be one or more selected from compounds represented by the following Chemical Formula 1, and in this case, when forming a thin film, a shielding region that does not remain in the thin film is formed to form a relatively sparse thin film, and side reactions are suppressed and the thin film growth rate is controlled to reduce process by-products in the thin film, thereby reducing corrosion and deterioration, and improving the crystallinity of the thin film. Even when a thin film is formed on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film can be significantly improved.

[0110] chemical formula 1

[0111] [ka]

[0112] (In the above Chemical Formula 1, R 1 and R 2 are each independently H or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 4.

[0113] In the above Chemical Formula 1, R 1 and R 2 is an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms. In this case, there are advantages such as a large effect of reducing process by-products and excellent step coverage, as well as an effect of improving the thin film density and further excellent electrical properties, insulating properties, and dielectric properties of the thin film.

[0114] In the above Chemical Formula 1, n is an integer of 1 to 4, preferably an integer of 1 to 3. In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the thin film density is improved, and the electrical properties, insulating properties, and dielectric properties of the thin film are further excellent.

[0115]

[0116] The step coverage improving agent may have, for example, a refractive index (measured at 20 to 25° C.) of 1.30 or more, 1.3 to 1.5, 1.35 to 1.48, or 1.36 to 1.46.

[0117] In this case, a deposition layer of uniform thickness due to the difference in the adsorption distribution degree of the step coverage improving agent having the above-mentioned structure is formed on the substrate as a shielding region that does not remain in the thin film, and the deposition speed of the thin film is reduced and the thin film growth rate is appropriately reduced, so that even when a thin film is formed under high temperature conditions on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved, and the adsorption of not only the thin film precursor but also the process by-products is prevented, thereby effectively protecting the surface of the substrate and effectively removing the process by-products.

[0118] In particular, since a relatively sparse thin film is formed and the growth rate of the formed thin film is significantly reduced, even when applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide effects such as being able to deposit a thin film and improving the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was previously difficult to reduce.

[0119]

[0120] The step coverage improver may include at least one compound selected from the compounds represented by the following formulas 1-1 to 1-7. In this case, the step coverage improver has a large effect of providing a thin film shielding region to control the thin film growth rate, a large effect of removing process by-products, and an excellent effect of improving step coverage and film quality, and the uniformity of the generated thin film may be significantly improved.

[0121] Chemical formula 1-1~1-7

[0122] [ka]

[0123] The amine compound is characterized by having a boiling point within a range of 5 to 200°C, specifically 10 to 90°C, and preferably 20 to 80°C. In this case, it not only improves the diffusibility of the step coverage improving agent, suppresses side reactions during thin film formation, adjusts the thin film growth rate, reduces process by-products in the thin film, reduces corrosion and deterioration, and improves the crystallinity of the thin film, but also reaches a stoichiometric oxidation state during the formation of a metal oxide film, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure under high temperature conditions.

[0124] The amine compound has, for example, a solubility in water (25° C.) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the amine compound has the advantages of low reactivity with precursor compounds and easy moisture management.

[0125] In this description, the solubility is not particularly limited to the measurement methods and standards commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by high performance liquid chromatography (HPLC).

[0126] The amine compound, preferably one or more alkylamines selected from the compounds represented by the following chemical formulas 3-1 to 3-5, or one or more arylamines selected from the compounds represented by the following chemical formulas 4-1 to 4-9, may have a deposition rate reduction rate of 5% or more, specifically 10% or more, as represented by the following formula 1. In this case, a deposition layer of a uniform thickness due to the difference in the adsorption distribution degree of the step coverage improving agent having the above-mentioned structure is formed as a shielding region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the formed thin film is significantly reduced. Therefore, even if applied to a substrate with a complex structure, 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 deposition can be performed with a thin thickness, and O, Si, metal, metal oxide, which remain as process by-products, and even carbon residues, which have been difficult to reduce in the past, can be improved.

[0127] Chemical formula 3-1~3-5

[0128] [ka]

[0129] Chemical formula 4-1~4-9

[0130] [ka]

[0131] Formula 1

[0132]

number

[0133] (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 the unit is Å / cycle.)

[0134] 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 measuring the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure, and then dividing the measured thickness by the total number of cycles to obtain an average deposition rate.

[0135] In the above formula 1, "when no thin film modification composition was used" refers to a case where a thin film is produced by adsorbing only a precursor compound onto a substrate in a thin film deposition process. A specific example of the thin film formation method is a case where a thin film is formed without adsorbing a thin film modification composition and purging unadsorbed thin film modification composition.

[0136]

[0137] The amine compound may be, for example, a compound having a refractive index of 1.30 or more, in the range of 1.30 to 1.70, 1.35 to 1.60, or 1.36 to 1.50.

[0138] In this case, by appropriately blocking the adsorption of the precursor compound to the substrate, the reaction rate is improved, and even when a thin film is formed on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film are significantly improved. In addition, the adsorption of not only the thin film precursor but also process by-products is prevented, thereby effectively protecting the substrate surface, and the process by-products can be effectively removed.

[0139]

[0140] The thin film modifying composition may contain the step coverage improver and the amine compound in a weight ratio of 50:50 to 99:1, more narrowly in a weight ratio of 60:40 to 95:5, preferably in a weight ratio of 70:30 to 92:8, and more preferably in a weight ratio of 80:20 to 90:10. In this case, a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced, so that even if it is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved, and in particular, it is possible to provide an effect that it is possible to provide an effect that it is possible to improve O, Si, metal, metal oxide, and even the carbon residue, which was difficult to reduce in the past, remaining as a process by-product, which are deposited at a thin thickness.

[0141] For reference, examples of the amine compound include dimethylethylamine having a boiling point of about 38°C, methylethylamine having a boiling point of about 33°C, and diethylamine having a boiling point of about 54.8°C.

[0142]

[0143] The thin film modifying composition may have a deposition rate reduction rate, represented by the following Equation 1, of 5% or more.

[0144] Formula 1

[0145]

number

[0146] (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 the unit is Å / cycle.)

[0147] The thin film shielding region is characterized in that it does not remain on the thin film.

[0148] Here, unless otherwise specified, "not remaining" refers to the presence of C element at 0.1 atomic % (atom %), Si element at less than 0.1 atomic % (atom %), N element at less than 0.1 atomic % (atom %), and halogen element at less than 0.1 atomic % (atom %) in the component analysis by XPS. More preferably, in the measurement method by secondary ion mass spectrometry (SIMS) in which the substrate is measured while being dug in the depth direction, or the measurement method by X-ray photoelectron spectroscopy (XPS), when the increase / decrease rate of C, N, Si, and halogen impurities before and after using the step coverage improving agent under the same deposition conditions is taken into consideration, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0149]

[0150] For example, the thin film may contain 100 ppm or less of halogen compounds. For reference, if an excessive amount of halogen remains, when a nitriding agent is used under the temperature condition of 200 to 300° C., which is the experimental condition described later, by-products such as NH4Cl are generated and remain in the thin film, which is not preferable.

[0151] The thin film may be used in a semiconductor device by improving step coverage during the formation process, for example, as an etching stop layer, an electrode layer, a dielectric layer, a gate insulating layer, a block oxide layer, or a charge trap, but is not limited thereto.

[0152] The thin film modifying composition may 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, impurities may remain in the thin film or cause side reactions with the precursor or reactant, so it is preferable to use a substance having a purity of 99% or more.

[0153]

[0154] The thin film modification composition is preferably used in an atomic layer deposition (ALD) process, in which case it has the advantage of being used as a thin film modification composition without interfering with the adsorption of precursor compounds, effectively protecting the surface of a substrate, and effectively removing process by-products.

[0155] The thin film modifying composition preferably 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 shielding 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.

[0156] More preferably, the thin film modifying composition has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.3g / cm 3The vapor pressure (20° C.) can be 1 to 260 mmHg. Within this range, the shielding 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.

[0157] In particular, since a relatively sparse thin film is formed and the growth rate of the formed thin film is significantly reduced, even when applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide effects such as being able to deposit a thin film and improving the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was previously difficult to reduce.

[0158]

[0159] The method for forming a thin film of the present invention is characterized by including a step of injecting the above-mentioned thin film modifying composition into a chamber to replace ligands of a precursor compound adsorbed on the surface of a loaded substrate. In this case, the ligands of the precursor adsorbed on the substrate are effectively replaced to improve the reaction rate and appropriately reduce the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure.

[0160]

[0161] In the step of shielding the surface of the substrate with the thin film modifying composition, the feeding time (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 excellent cost-effectiveness.

[0162] 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.

[0163]

[0164] As a preferred embodiment, the thin film forming method may include the steps of: i) vaporizing the thin film modifying composition to shield the surface of a substrate loaded into a chamber; ii) performing a first purge of the interior of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it in an area outside the shielded area; iv) performing a second purge of the interior of the chamber with a purge gas; v) supplying a reaction gas into the interior of the chamber; and vi) performing a third purge of the interior of the chamber with a purge gas.

[0165] In this case, steps i) to iv) are regarded as a unit cycle, and the cycle can be repeated until a thin film having a desired thickness is obtained (see FIG. 1 below). When the thin film modifying composition of the present invention is added prior to the precursor compound in one cycle to improve the film quality, even if the deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, and the process by-products generated are effectively removed, reducing the resistivity of the thin film and significantly improving the step coverage.

[0166] 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.

[0167]

[0168] 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.

[0169] 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, 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 shielding region by the thin film modifying composition can be maximized despite natural oxidation.

[0170] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

[0171] The thin film may be a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a tellurium oxide film.

[0172] In the present invention, the precursor compound or the precursor compound may include a step of plasma post-treatment after being vaporized and injected, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0173]

[0174] When the precursor compound is adsorbed while injecting the thin film modifying composition onto the substrate, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed 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 may be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed 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 the 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 vapor.

[0175] As a specific example, in the step of injecting the thin film modifying composition (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 seconds, and purging the unadsorbed thin film modifying composition, a purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 seconds, and the amount of purge gas injected is 602 times the amount of the thin film modifying composition injected.

[0176]

[0177] The amount of purge gas introduced into the chamber in the step of purging the unadsorbed precursor compound 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, and more preferably 100 to 10,000 times 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.

[0178] 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, and more preferably 100 to 10,000 times the volume of the reaction gas introduced into the chamber, and the desired effect can be sufficiently obtained within this range. Here, the amounts of the purge gas and reaction gas introduced are each based on one cycle.

[0179]

[0180] 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 delivered into the chamber by the LDS method.

[0181] 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 in an unheated state 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.

[0182]

[0183] The ratio of the amount (mg / cycle) of the thin film modifying composition to the amount (mg / cycle) of the precursor compound fed into the chamber 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.

[0184]

[0185] The precursor materials may be used in combination with a non-polar solvent.

[0186] As the non-polar solvent, an alkane or cycloalkane having 1 to 5 carbon atoms can be used, and specifically, the non-polar solvent may comprise 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0187] Even if the above-mentioned types of non-polar solvents are used, if the amount of the organic solvent used exceeds the upper limit, impurities are introduced, increasing the resistance and the impurity value in the thin film. If the content of the organic solvent is less than the lower limit, the effect of improving step coverage and the effect of reducing impurities such as chlorine (Cl) ions by adding the solvent are not obtained.

[0188]

[0189] In the thin film forming method, when the thin film modifying composition is used, the deposition rate reduction rate represented by the following formula 1 may be 5% or more, specifically 10% or more. In this case, a deposition layer having a uniform thickness due to the difference in the adsorption distribution degree of the step coverage improving agent having the above-mentioned structure is formed as a replacement region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the method is applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide an effect that the deposition can be performed 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.

[0190] Formula 1

[0191]

number

[0192] (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 the unit is Å / cycle.)

[0193]

[0194] In the thin film forming method, when the thin film modifying composition is used, the degree of non-uniformity shown in the following formula 2 can be 1% or less, specifically 0.5% or less, preferably 0.01 to 0.2%. In this case, a deposition layer of a uniform layer thickness due to the difference in the adsorption distribution degree of the step coverage improving agent having the above-mentioned structure is formed as a replacement region that does not remain in the thin film, and a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the method is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide an effect that the deposition can be performed with a thin thickness, and the amount of O, Si, metal, metal oxide, and even the amount of carbon remaining as process by-products, which have been difficult to reduce in the past, can be improved.

[0195] Equation 2

[0196]

number

[0197] The maximum and minimum film thicknesses were selected by measuring the thin film using the ellipsometer apparatus used for the deposition rate reduction rate described above.

[0198] As an example, the thickness can be selected by measuring the film thickness at ten arbitrarily selected locations, and preferably, the thickness can be selected by measuring the film thickness at four locations on the north, south, east and west edges of a 300 mm wafer and one location in the center.

[0199]

[0200] 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, 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 this range, the effect of preventing corrosion and deterioration is outstanding.

[0201] 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.

[0202]

[0203] 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.

[0204] 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, and further preferably at a deposition temperature in the range of 400 to 600°C. Within this range, there is an effect of growing a thin film with excellent film quality while realizing the ALD process characteristics.

[0205] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, there is an effect that a thin film with a uniform thickness can be obtained.

[0206] 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.

[0207] The thin film forming method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the thin film modifying composition into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the thin film modifying composition into the chamber.

[0208] 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 thin film modifying composition, a first transport means for transporting the vaporized thin film modifying composition 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 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.

[0209] The first vaporizer for vaporizing the thin film modifying composition may be divided into at least two types, such as a vaporizer for vaporizing a step coverage improving agent and a vaporizer for vaporizing an amine compound, as necessary.

[0210] As a specific example, the method of forming the thin film will be described. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of depositing atomic layers.

[0211] The substrate may be a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0212] The substrate may further have a conductive or insulating layer formed thereon.

[0213] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned thin film modifying composition and a precursor compound or a mixture thereof with a non-polar solvent are prepared.

[0214] Then, the prepared thin film modifying composition (e.g., a step coverage improving agent and an amine compound) is injected into a vaporizer, converted into a vapor phase, and delivered to a deposition chamber to be adsorbed onto a substrate, and then purged to remove any unadsorbed thin film modifying composition.

[0215] Next, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (a composition for forming a thin film) is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber where it is adsorbed onto a substrate. The precursor compound is then shielded by a step coverage improving agent that was injected in advance, and any unadsorbed precursor compound or the mixture of the precursor compound and the non-polar solvent is purged.

[0216] In this description, as a method for delivering the thin film modifying composition and the precursor compound (composition for forming a thin film) to the deposition chamber, for example, a method for delivering a volatilized gas using a mass flow controller (MFC) method (Vapor Flow Control: VFC) or a method for delivering a liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System: LDS) can be used, and preferably the LDS method can be used.

[0217] In this case, the carrier gas or dilution gas for transferring the thin film modifying composition and the precursor compound, etc. onto the substrate may be one or a mixture of two or more gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0218] In this description, the purge gas may be, for example, an inert gas, and preferably the above-mentioned carrier gas or dilution gas.

[0219]

[0220] Then, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably include a nitriding agent. The nitriding agent reacts with a precursor compound adsorbed on the substrate to form a nitride film.

[0221] Preferably, the nitriding agent can be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas.

[0222] The remaining unreacted reactant gas is then purged with an inert gas, which removes not only the excess reactant gas but also any by-products that are produced.

[0223] As described above, the thin film formation method, for example, includes a unit cycle including the steps of supplying a thin film modifying composition onto a substrate, purging unadsorbed thin film modifying composition, adsorbing a precursor compound / thin film forming composition onto a substrate, purging unadsorbed precursor compound, adsorbing an amine compound onto a substrate, purging unadsorbed amine compound, supplying a reactive gas, and purging residual reactive gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0224] The unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and further preferably 100 to 2,000 times. Within this range, the desired thin film properties can be effectively exhibited.

[0225]

[0226] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described above, and in this case, the thin film has excellent step coverage and thickness uniformity, and has excellent thin film density and electrical properties.

[0227]

[0228] The produced thin film may preferably 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, there is an effect of excellent thin film properties.

[0229] 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.

[0230] 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 of being applicable to next-generation semiconductor devices.

[0231] 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 excellent performance as a dielectric film or blocking film, but is not limited thereto.

[0232]

[0233] 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.

[0234] 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.

[0235] The intermediate layer is, for example, Ti x N y , preferably TN.

[0236] The upper layer film may contain, for example, one or more selected from the group consisting of W and Mo.

[0237]

[0238] Below, preferred embodiments and drawings are presented to aid in understanding the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications 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.

[0239]

[0240] EXAMPLES

[0241] Examples 1 to 2, Comparative Examples 1 to 3

[0242] An ALD deposition process was carried out according to FIG. 1 below using the components shown in Table 1 below.

[0243] FIG. 1 is a schematic diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0244] Specifically, as the step coverage improving agent, a compound represented by the following chemical formula 1-1 (corresponding to MG) and a compound represented by the following chemical formula 1-2 (corresponding to DMC) were prepared, and as the amine compound, a compound represented by the following chemical formula 3-3 (corresponding to DMEA) was prepared.

[0245] Chemical formula 1-1

[0246] [ka]

[0247] Chemical formula 1-2

[0248] [ka]

[0249] Chemical formula 3-3

[0250] [ka]

[0251] As a thin film modifying composition, 90 parts by weight of the compound represented by the above formula 1-1 and 10 parts by weight of the compound represented by the above formula 3-3 were mixed and shown as composition 1 in Table 1 below.

[0252] As a thin film modifying composition, 90 parts by weight of the compound represented by the above formula 1-2 and 10 parts by weight of the compound represented by the above formula 3-3 were mixed and shown as composition 2 in Table 1 below.

[0253] In addition, trimethylaluminum (shown as "TMA" in the table below) was prepared as a precursor.

[0254] As shown in FIG. 1 below, argon was flowed into the chamber at 5000 ml / min while the pressure inside the chamber was adjusted to 1.5 Torr using a vacuum pump to form a dilute inert atmosphere.

[0255] The thin film modifying composition shown in Table 1 below was placed in a canister, and the partial pressure and temperature were adjusted to the injection amount (mg / cycle). The composition was then loaded into a deposition chamber with a substrate loaded therein for 1 second to coat the substrate, and the chamber was purged for 10 seconds.

[0256] Next, the precursor compound was put into a canister and introduced into the deposition chamber using a vapor flow controller (VFC) as shown in Table 1 below, and then argon gas was supplied at 5000 sccm for 2 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0257] Next, the reactive gas O2 is mixed with O3 at a concentration of 200 g / m 3 The mixture was placed in a deposition chamber as shown in Table 1 below, and the chamber was purged for 10 seconds. At this time, the substrate on which the thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0258] This process was repeated 100 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0259] For each of the obtained thin films of Examples 1 and 2 and Comparative Examples 1 to 3, the deposition rate reduction rate (D / R reduction rate), secondary ion mass spectrometry (SIMS) C impurities, and step coverage were measured by the following method.

[0260]

[0261] * Deposition rate reduction rate (D / R (dep.rate) reduction rate): This refers to the ratio of the deposition rate reduction after the introduction of the shield compared to the D / R before the introduction of the thin film modifying composition, and was calculated as a percentage using the measured Å / cycle values.

[0262] Specifically, the film thickness of the thin film was measured using an ellipsometer, which is a device capable of measuring optical properties such as the film thickness and refractive index of the thin film using the polarization properties of light, and divided by the number of cycles to calculate the film thickness deposited per cycle, and the reduction rate of the thin film growth rate was calculated. Specifically, it was calculated using the following Equation 1.

[0263] Formula 1

[0264]

number

[0265] (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 the unit is Å / cycle.)

[0266]

[0267] *The non-uniformity was calculated by selecting the maximum and minimum film thicknesses among those measured by the ellipsometer and using the following Equation 2, and the results are shown in Table 1 and Figure 2. Specifically, the film thickness was measured at four points on the north, south, east and west edges of a 300 mm wafer and at one point in the center.

[0268] Equation 2

[0269]

number

[0270] * SIMS (Secondary-ion mass spectrometry) C impurity: The C impurity value in the SIMS graph was confirmed by taking into consideration the C impurity counts when the thin film was axially excavated by ion sputtering and the sputtering time was 50 seconds, which is the least contaminated part of the surface layer of the substrate.

[0271] [Table 1]

[0272] As shown in Table 1, it was confirmed that in Examples 1 and 2, in which the thin film modifying composition according to the present invention was used, the reduction rate of the deposition rate was equal or similar to that in Comparative Examples 1 to 3, in which the thin film modifying composition according to the present invention was not used, and the degree of non-uniformity was significantly improved. In particular, it was confirmed that in Examples 1 and 2, in which the thin film modifying composition according to the present invention was used, the degree of non-uniformity was significantly better than that in Comparative Example 1, in which the thin film modifying composition according to the present invention was not used, or Comparative Examples 2 and 3, in which the step coverage improving agent was used alone.

[0273] Specifically, as shown in FIG. 2 below, the calculated non-uniformity in Examples 1 and 2 using the thin film modifying composition according to the present invention was less than 1%, whereas the calculated non-uniformity in Comparative Examples 2 and 3 not using an amine compound was 3% or more, reaching a maximum of 7%.

Claims

1. A thin film modifying composition comprising 50 to 99 parts by weight of a step coverage improving agent including a compound represented by the following formula 1, and 1 to 50 parts by weight of an amine compound, wherein the amine compound is at least one selected from the group consisting of alkylamines having a boiling point in the range of 5 to 200°C and arylamines having a boiling point in the range of 50 to 260°C. Chemical formula 1 【Chemistry 1】 (In the above Chemical Formula 1, R １ and R ２ are each independently H or an alkyl group having 1 to 5 carbon atoms, and n is an integer from 1 to 4.

2. The thin film modifying composition according to claim 1, wherein the step coverage improving agent comprises at least one compound selected from the group consisting of compounds represented by the following formulas 1-1 to 1-7: Chemical formula 1-1 to 1-7 【Chemistry 2】

3. The thin film modifying composition according to claim 1 , wherein the amine compound is a compound represented by the following formula 3: chemical formula 3 【Chemistry 3】 (In the above Chemical Formula 3, R ３ , R ４ and R ５ are each independently selected from H, an alkane having 1 to 5 carbon atoms, an alkene having 1 to 5 carbon atoms, an alkane having 1 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms; R ３ , R ４ , R ５ Two or more of these may be linked together to form a cyclic structure.

4. The thin film modifying composition according to claim 1, wherein the alkylamine is at least one selected from the compounds represented by the following formulas 3-1 to 3-5: Chemical formulas 3-1 to 3-5 【Chemistry 4】

5. The thin film modifying composition according to claim 1, wherein the arylamine is at least one selected from the compounds represented by the following formulas 4-1 to 4-9: Chemical formulas 4-1 to 4-9 【Chemistry 5】

6. The thin film is characterized in that the step coverage is improved during the formation of a laminate film 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. The thin film modifying composition according to claim 1.

7. The method includes injecting a thin film modifying composition including 50 to 99 parts by weight of a step coverage improving agent including a compound represented by the following Formula 1 and 1 to 50 parts by weight of an amine compound into a chamber to shield a surface of a loaded substrate, The amine compound is at least one selected from the group consisting of alkylamines having a boiling point in the range of 5 to 200°C and arylamines having a boiling point in the range of 50 to 260°C. Chemical formula 1 【Chemistry 6】 (In the above Chemical Formula 1, R １ and R ２ are each independently H or an alkyl group having 1 to 5 carbon atoms, and n is an integer from 1 to 4.

8. 8. The method of claim 7, 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.

9. 8. The method of claim 7, wherein the thin film modifying composition is delivered into the chamber by a vapor flow control (VFC), direct liquid introduction (DLI) or liquid delivery system (LDS) method, and the thin film is a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film or an aluminum oxide film.

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

11. 11. The semiconductor substrate according to claim 10, wherein the thin film has a multi-layer structure of two or more layers.

12. A semiconductor device comprising the semiconductor substrate of claim 11.

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