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 present invention has the effect of improving the step coverage and the uniformity of the thin film thickness even when a thin film is formed under high temperature conditions on a substrate having a complex structure by improving the reaction rate and appropriately reducing the thin film growth rate by using a shielding material and a diffusion improving material in combination, and improving the film quality by reducing impurities.

Description

[Technical field]

[0001] 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. More specifically, the present invention relates to a thin film modification composition comprising a shielding material and a diffusion improving material, which effectively shields a substrate even under high temperature conditions to improve the reaction rate, and appropriately reduces 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, and also relates to a thin film modification composition that significantly reduces impurities and improves film quality, a thin film formation method using the same, and a semiconductor substrate manufactured thereby. [Background technology]

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

[0003] As one example, the ratio of width to depth of a microstructure (hereinafter also referred to as the "aspect ratio") is becoming greater than 20:1 and greater than 100:1, and the larger the aspect ratio becomes, 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 shielding agent is used to mitigate the increase in GPC associated with 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 effect of reducing GPC using the conventionally known shielding agents.

[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 shielding material in combination with a diffusion improving material 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, electrical properties, and dielectric properties of a thin film by improving the crystallinity and oxidation fraction of the thin film.

[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 composition comprising: 50 to 99 parts by weight of a shielding material having one or more unshared electron pairs selected from oxygen (O), sulfur (S), and phosphorus (P); and 1 to 50 parts by weight of a diffusion improving material;

[0014] The diffusion-improving substance has a boiling point in the range of 5 to 200°C.

[0015] The shielding material may include linear or cyclic, saturated or unsaturated hydrocarbons having two or more oxygen (O), phosphorus (P) or sulfur (S) atoms and having 3 to 15 carbon atoms.

[0016] The shielding material may include compounds having a structure containing oxygen (O), phosphorus (P), or sulfur (S) at either end of a central carbon atom connected to oxygen by a double bond.

[0017] The shielding material may include compounds having a structure containing oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to an oxygen by a double bond and carbon (C) at the other end.

[0018] The shielding substance may be at least one selected from the compounds represented by the following Chemical Formula 1 to 2.

[0019] [Chemical formula 1]

[0020] [ka]

[0021] [Chemical formula 2]

[0022] [ka]

[0023] (In the above Chemical Formulas 1 and 2, R′ and R ” each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

[0024] A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH2;

[0025] B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3;

[0026] m is an integer from 0 to 3.

[0027] The shielding substance may include one or more compounds selected from the compounds represented by the following chemical formulas 1-1 to 1-4 and 2-1 to 2-4.

[0028] [Chemical formula 1-1~1-6]

[0029] [ka]

[0030] [Chemical formula 2-1~2-4]

[0031] [ka]

[0032] The shielding material may have a refractive index (measured at 20-25° C.) of 1.30 or more, 1.3-1.5, 1.35-1.48, or 1.36-1.46.

[0033]

[0034] The diffusion improving substance may have a boiling point in the range of 5 to 200°C, specifically 10 to 150°C, and preferably 25 to 140°C.

[0035] The diffusion-improving substance may preferably be a liquid type at room temperature in order to improve the diffusion and uniformity of the above-mentioned shielding substance.

[0036] The diffusion improving substance may be one or more selected from the group consisting of octane, diethyl ether, methylene chloride, toluene, hexane, and ethanol.

[0037] The diffusion improving material may have a refractive index of 1.30 or more, 1.30 to 1.70, 1.35 to 1.60, or 1.36 to 1.50.

[0038]

[0039] The thin film modifying composition may have a deposition rate reduction rate, represented by the following Equation 1, of 30% or more.

[0040] [Formula 1]

[0041] TIFF2025510866000006.tif9138

[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 the addition of any diffusion improving material. DR f (Final deposition rate) is the deposition rate of a thin film formed by adding a diffusion improving material 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.)

[0043] The thin film may be 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.

[0044] 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 block oxide film, or a charge trap.

[0045]

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

[0047] The present invention provides a method for forming a thin film, comprising the steps of injecting a thin film modification composition containing 50 to 99 parts by weight of a shielding material having one or more unshared electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P) and 1 to 50 parts by weight of a diffusion improving material into a chamber to shield the surface of a substrate that has been loaded, wherein the diffusion improving material 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.

[0048] The precursor compound used in the thin film formation method may be a compound represented by the following Chemical Formula 3.

[0049] [Chemical formula 3]

[0050] [ka]

[0051] (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 L4 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-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.)

[0052] As an example, when the central metal is divalent, L 1 and L 2can 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] In the above formula 3, 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.

[0054] In the above Chemical Formula 3, 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.

[0055] In the above 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.

[0056]

[0057] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0058] i) vaporizing said thin film modifying composition to mask the surface of the substrate loaded in the chamber;

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

[0060] iii) vaporizing a precursor compound and allowing it to adsorb in an area outside the shielded 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 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.

[0065] 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.

[0066] After the thin film modification composition or precursor compound has been vaporized and injected, a plasma post-treatment step may be included.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The present invention also provides a semiconductor substrate produced by the above-mentioned thin film formation method.

[0072] The thin film may have a multi-layer structure of two or more layers.

[0073]

[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 step coverage and density of the thin film can be improved, and further, a thin film forming 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.

[0081] [Diagram 3] 3 is a TEM photograph showing the measurement of step coverage at the top and bottom ends of a thin film obtained in Example 1 described later. [Figure 4] 1 is a TEM photograph showing the measurement of step coverage at the top and bottom ends of a thin film obtained in Example 2 described later. [Diagram 5] 1 is a TEM photograph showing the measurement of step coverage at the top and bottom ends of a thin film obtained in Example 3 described below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0082]

[0083] 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.

[0084] 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.

[0085] In this description, the term "diffusion improving material" means, unless otherwise specified, a material that can aid the diffusion of the shielding material and improve the uniformity.

[0086] The present inventors have found that, in order to form a thin film on the surface of a substrate loaded inside a chamber, a shielding material capable of shielding the adsorption of a precursor compound to be supplied and a diffusion improving material capable of modifying the uniformity of the thin film formed are 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 is improved, the uniformity of the thin film is ensured, and the step coverage is greatly improved, and in particular, it is possible to deposit a thin film, 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 it into research on a thin film modifying composition.

[0087]

[0088] 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.

[0089] 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.

[0090] The thin film means that the film composition contains SiH and SiOH.

[0091] 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 block oxide film, or a charge trap.

[0092]

[0093] The precursor compound used to form a thin film in the present invention is a molecule having a central metal atom (M) 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, or Nd, and one or more ligands consisting of C, N, O, H, and X (halogens), and when the precursor has a vapor pressure of 1 mTorr to 100 Torr at 25° C., the film quality improvement effect described below can be maximized.

[0094] As an example of the precursor compound, a compound represented by the following Chemical Formula 3 can be used.

[0095] [Chemical formula 3]

[0096] [ka]

[0097] (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 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-C 10 and may be linear or cyclic.

[0098] In the formula 3, M is hafnium (Hf), silicon (Si), zirconium (Zr) or aluminum (Al), preferably hafnium (Hf) or silicon (Si). 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, insulation properties and dielectric properties of the thin film are further excellent.

[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 L1 , L 2 , L 3 and L 4 are -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 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.

[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] Examples of aluminum precursor compounds include trimethyl aluminum (TMA), tris(dimethylamido)aluminum (TDMAA), and aluminum trichloride (AlCl3).

[0105] etc. can be used.

[0106]

[0107] The thin film modifying composition may be comprised of a shielding material and a diffusion improving material.

[0108] Here, the shielding material is characterized by including 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, and process by-products in the thin film are reduced to reduce corrosion and deterioration, the crystallinity of the thin film is improved, a stoichiometric oxidation state is reached during the formation of a metal oxide film, and even when a thin film is formed on a substrate having a complex structure under high temperature conditions, step coverage and thickness uniformity of the thin film are significantly improved.

[0109] As a specific example, the shielding material 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 the thin film density and excellent electrical properties of the thin film.

[0110] Here, unless otherwise specified, the structure containing oxygen (O), phosphorus (P) or sulfur (S) at both ends of the central carbon atom connected to the oxygen by a double bond is [ka] Refers to...

[0111] Specifically, the shielding material has a structure in which one end of a central carbon atom connected to oxygen by a double bond contains oxygen (O), phosphorus (P) or sulfur (S) and the other end contains carbon (C), thereby providing a large reduction in process by-products, excellent step coverage, and excellent thin film density improvement and electrical properties.

[0112] Here, unless otherwise specified, the structure containing oxygen (O), phosphorus (P) or sulfur (S) at one end of the central carbon atom connected to the oxygen by a double bond and carbon (C) at the other end is [ka] Refers to...

[0113] As a specific example, the shielding material may be one or more selected from the compounds represented by the following formulas 1 to 2. 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.

[0114] [Chemical formula 1]

[0115] [ka]

[0116] [Chemical formula 2]

[0117] [ka]

[0118] (In the above Chemical Formulas 1 and 2, R′ and R ”each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

[0119] A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH2;

[0120] B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3;

[0121] m is an integer from 0 to 3.

[0122] In the above Chemical Formula 1, A is oxygen (O) or sulfur (S), and preferably oxygen (O). 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, insulating properties, and dielectric properties of the thin film are further excellent.

[0123] The R' is an alkyl group having 1 to 3 carbon atoms, and preferably an alkyl group having 1 to 2 carbon atoms. 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, insulation properties, and dielectric properties of the thin film are further excellent.

[0124] The above m is an integer of 1 to 2, and is preferably an integer of 1.

[0125] In Formula 2, B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3. 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.

[0126] The R″ is an alkyl group having 1 to 3 carbon atoms, and preferably an alkyl group having 1 to 2 carbon atoms. 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.

[0127]

[0128] When the shielding material is, for example, a compound represented by Chemical Formula 1, it may be a compound having a refractive index in the range of 1.4 to 1.5, specifically 1.4 to 1.48, and preferably 1.4 to 1.46.

[0129] When the shielding substance is, for example, a compound represented by Chemical Formula 2, it may be a compound having a refractive index in the range of 1.3 to 1.4, specifically 1.33 to 1.39, and preferably 1.35 to 1.39.

[0130]

[0131] In this case, a deposition layer of uniform thickness due to the difference in the adsorption distribution degree of the shielding 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.

[0132] 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.

[0133]

[0134] The shielding material may include at least one compound selected from the compounds represented by the following formulae 1-1 to 1-4 and 2-1 to 2-4. In this case, it is possible to provide a thin film shielding region, thereby controlling the thin film growth rate, removing process by-products, improving step coverage and film quality, and significantly improving the uniformity of the thin film.

[0135] [Chemical formula 1-1~1-4]

[0136] [ka]

[0137] [Chemical formula 2-1~2-4]

[0138] [ka]

[0139] The diffusion improving material has a boiling point within a range of 5-200°C, 5-190°C, or 6-190°C. In this case, the diffusion improving material improves the diffusivity of the shielding material, suppresses side reactions during thin film formation, controls 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. In addition, the diffusion improving material can reach a stoichiometric oxidation state during the formation of a metal oxide film, and can significantly improve step coverage and thickness uniformity of the thin film even when the thin film is formed on a substrate having a complex structure under high temperature conditions.

[0140] The diffusion improving substance 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 diffusion improving substance has the advantages of low reactivity with precursor compounds and easy moisture control.

[0141] 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).

[0142] The diffusion improving material, preferably at least one selected from octane, diethyl ether and methylene chloride, may have a deposition rate reduction rate represented by the following mathematical formula 1 of 30% or more, specifically 40% or more, preferably 50% or more. In this case, a deposition layer of a uniform thickness due to the difference in the adsorption distribution degree of the activator 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 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.

[0143] [Formula 1]

[0144] TIFF2025510866000015.tif13148

[0145] (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 the addition of any diffusion improving material. DR f (final deposition rate) is the deposition rate of the thin film formed by adding the diffusion improving material when the above-mentioned process is carried out. Here, the deposition rate (DR) is the value measured by using an ellipsometer device under conditions of room temperature and normal pressure for a thin film with a thickness of 3 to 30 nm, and the unit is Å / cycle.)

[0146] 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.

[0147] 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.

[0148] The diffusion-improving substance 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.

[0149] 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.

[0150]

[0151] The thin film modifying composition may contain the shielding material and the diffusion improving material 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.

[0152] For reference, the diffusion improving substances include octane, which has a boiling point of about 125.6°C, methylene chloride, which has a boiling point of about 39.6°C, and diethyl ether, which has a boiling point of about 34.6°C.

[0153]

[0154] The thin film modifying composition may have a deposition rate reduction rate, represented by the following Equation 1, of 30% or more.

[0155] [Formula 1]

[0156] TIFF2025510866000016.tif13169

[0157] (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 the addition of any diffusion improving material. DR f(final deposition rate) is the deposition rate of the thin film formed by adding the diffusion improving material when the above-mentioned process is carried out. Here, the deposition rate (DR) is the value measured by using an ellipsometer device under conditions of room temperature and normal pressure for a thin film with a thickness of 3 to 30 nm, and the unit is Å / cycle.)

[0158] The thin film shielding region is characterized in that it does not remain on the thin film.

[0159] 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), considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using an activator 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%.

[0160]

[0161] 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 1.2% or less, specifically 1.1% or less, preferably 0.01 to 1.1%. 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, 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 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.

[0162] [Formula 2]

[0163] TIFF2025510866000017.tif11146

[0164] 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.

[0165] 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.

[0166]

[0167] 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.

[0168] The thin film can be used as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap, but is not limited to these.

[0169] The thin film modifying composition 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, 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.

[0170]

[0171] 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.

[0172] 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, there are effects such as excellent step coverage, thin film thickness uniformity, and improved film quality.

[0173] 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 3 The vapor pressure (20° C.) can be 1 to 260 mmHg. Within this range, there are effects such as excellent step coverage, thin film thickness uniformity, and improved film quality.

[0174]

[0175] 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.

[0176]

[0177] 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.

[0178]

[0179] In the step of shielding the surface of the substrate with the thin film modification composition, the feeding time (seconds (sec)) of the thin film modification composition to the surface of the substrate is preferably 0.01 to 10 seconds 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.

[0180] 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.

[0181]

[0182] In 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 the substrate loaded into the chamber, ii) purging the inside of the chamber with a purge gas, iii) vaporizing the precursor compound and adsorbing it to an area outside the shielding area, iv) purging the inside of the chamber with a purge gas, v) supplying a reaction gas into the chamber, and vi) purging the inside of the chamber with a purge gas. At this time, the steps i) to vi) are regarded as a unit cycle, and the cycle can be repeated until a thin film of a desired thickness is obtained (see FIG. 1 below). In this way, when the thin film modifying composition of the present invention is introduced before 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 resistivity of the thin film can be reduced by effectively removing the process by-products generated, thereby significantly improving the step coverage.

[0183] 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 be adsorbed onto a 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 when 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.

[0184]

[0185] 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.

[0186]

[0187] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

[0188] In the present invention, the thin film modifying composition or precursor compound may include a step of plasma post-treatment after vaporization and injection, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0189]

[0190] 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.

[0191] 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.

[0192]

[0193] 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.

[0194]

[0195] 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.

[0196]

[0197] 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.

[0198] The substrate loaded in the chamber may be heated to, for example, 50 to 400°C, specifically 50 to 400°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 according to deposition efficiency, for example, at 50 to 400°C for 1 to 20 seconds.

[0199]

[0200] 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.

[0201]

[0202] The precursor materials may be used in combination with a non-polar solvent.

[0203] 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.

[0204] 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.

[0205]

[0206] 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 can be 30% or more, specifically 35% or more. In this case, a deposition layer having a uniform thickness due to the difference in the adsorption distribution degree of the activator 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 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 at a thin thickness, and O, Si, metal, metal oxide, and even carbon residues that were left as process by-products and were difficult to reduce in the past can be improved.

[0207] [Formula 1]

[0208] TIFF2025510866000018.tif10135

[0209] (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 the addition of any diffusion improving material. DR f(final deposition rate) is the deposition rate of the thin film formed by adding the diffusion improving material when the above-mentioned process is carried out. Here, the deposition rate (DR) is the value measured by using an ellipsometer device under conditions of room temperature and normal pressure for a thin film with a thickness of 3 to 30 nm, and the unit is Å / cycle.)

[0210]

[0211] 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.

[0212] 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.

[0213]

[0214] 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.

[0215] 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 100 to 700°C, more preferably at a deposition temperature in the range of 200 to 650°C, and further preferably at a deposition temperature in the range of 220 to 400°C. Within this range, there is an effect of growing a thin film with excellent film quality while realizing the ALD process characteristics.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] 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 shielding material and a vaporizer for vaporizing a diffusion improving material, as necessary.

[0221] 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.

[0222] The substrate may be a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0223] The substrate may further have a conductive or insulating layer formed thereon.

[0224] 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.

[0225] Then, the prepared thin film modifying composition (e.g., a shielding material) is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto a substrate, followed by purging to remove any unadsorbed thin film modifying composition.

[0226] 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 shielded by a shielding material that was previously injected, and any unadsorbed precursor compound or a mixture of the precursor compound and a non-polar solvent is purged.

[0227] 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.

[0228] 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.

[0229] In this description, the purge gas may be, for example, an inert gas, and preferably the above-mentioned carrier gas or diluent gas.

[0230]

[0231] 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.

[0232] Preferably, the nitriding agent can be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas.

[0233] 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.

[0234] As described above, the thin film formation method, for example, includes a unit cycle including the steps of supplying a shielding material onto a substrate, purging unadsorbed shielding material, adsorbing a precursor compound / thin film formation composition onto a substrate, purging unadsorbed precursor compound, adsorbing a diffusion improvement material onto a substrate, purging unadsorbed diffusion improvement material, 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.

[0235] 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.

[0236]

[0237] 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.

[0238]

[0239] The thin film thus produced preferably has a thickness of 20 nm or less, a resistivity of 50 to 400 μΩ·cm based on a thin film thickness of 10 nm, a halogen content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within these ranges, the thin film has excellent performance as a diffusion barrier film and has the effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0240] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 25 nm, and even more preferably 5 to 20 nm, and within this range, there is an effect of excellent thin film properties.

[0241] For example, the thin film may have a resistivity of 0.1 to 400 μΩ·cm, preferably 15 to 300 μΩ·cm, more preferably 20 to 290 μΩ·cm, and even more preferably 25 to 280 μΩ·cm, based on a thin film thickness of 10 nm. Within this range, the thin film has the effect of having excellent thin film properties.

[0242] The thin film may have a halogen content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm. Within this range, the thin film has excellent thin film properties while having a reduced thin film growth rate. Here, the halogen remaining in the thin film may be, for example, Cl2, Cl, or Cl. - The lower the amount of residual halogen in the thin film, the better the film quality, which is preferable.

[0243] 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.

[0244] The thin film thus produced preferably has a thickness of 20 nm or less, a carbon, nitrogen, and halogen content of 10,000 ppm or less based on a thickness of 10 nm, and a step coverage rate of 90% or more. Within these ranges, the thin film has the effect of exhibiting excellent performance as a dielectric film or a blocking film, but is not limited thereto.

[0245]

[0246] The thin film may have a multilayer structure of two or three layers, preferably a multilayer structure of two or three layers, as required, for example. The multilayer film of the two-layer structure may have a lower layer film-middle layer film structure as a specific example, and the multilayer film of the three-layer structure may have a lower layer film-middle layer film-upper layer film structure as a specific example.

[0247] 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.

[0248] The intermediate layer is, for example, Ti x N y , preferably TN.

[0249] The upper layer film may contain, for example, one or more selected from the group consisting of W and Mo.

[0250]

[0251] 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.

[0252]

[0253] EXAMPLES

[0254] Examples 1 to 3, Comparative Examples 1 to 2

[0255] An ALD deposition process was carried out according to FIG. 1 below using the components shown in Table 1 below.

[0256] FIG. 1 is a schematic diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0257] Specifically, a compound represented by the following chemical formula 2-1 was prepared as the shielding substance, and a compound represented by the following chemical formula 4-1, a compound represented by the following chemical formula 4-2, and a compound represented by the following chemical formula 4-3 were prepared as the diffusion improving substance.

[0258] [Chemical formula 2-1]

[0259] [ka]

[0260] [Chemical formula 4-1]

[0261] [ka]

[0262] [Chemical formula 4-2]

[0263] [ka]

[0264] [Chemical formula 4-3]

[0265] [ka]

[0266] As a thin film modifying composition, 90 parts by weight of the compound represented by the above formula 2-1 and 10 parts by weight of the compound represented by the above formula 4-1 were mixed and shown as composition 1 in Table 1 below.

[0267] As a thin film modifying composition, 90 parts by weight of the compound represented by the above formula 2-1 and 10 parts by weight of the compound represented by the above formula 4-2 were mixed and shown as composition 2 in Table 1 below.

[0268] As a thin film modifying composition, 80 parts by weight of the compound represented by the above formula 2-1 and 20 parts by weight of the compound represented by the above formula 4-3 were mixed and shown as composition 3 in Table 1 below.

[0269]

[0270] In addition, trimethylaluminum (shown as "TMA" in the table below) was prepared as a precursor.

[0271] As shown in Figure 1 below, the prepared thin film modifying composition, or shielding material or diffusion improving material was placed in a canister and supplied to a vaporizer heated to 150°C at a flow rate of 0.05g / min using a liquid mass flow controller (LMFC) at room temperature. The shielding material vaporized in the vapor phase in the vaporizer was introduced into a deposition chamber loaded with a substrate for 1 second, and then argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.5Torr.

[0272] Next, the precursor was placed in a canister and introduced into the deposition chamber using a vapor flow controller (VFC) as shown in Table 1, 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.

[0273] Next, 1000 sccm of ozone as a reactive gas was introduced into the reaction chamber for 3 seconds, and then argon purging was performed for 3 seconds. At this time, the substrate on which the metal thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0274] This process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0275] For each of the obtained thin films of Examples 1 to 3 and Comparative Examples 1 and 2, the deposition rate reduction rate (D / R reduction rate), secondary ion mass spectrometry (SIMS) C impurities, and step coverage were measured by the following methods.

[0276] * 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 thin film modifying composition 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 value.

[0277] 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.

[0278] [Formula 1]

[0279] TIFF2025510866000023.tif11135

[0280] (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 the addition of any diffusion improving material. DR f (final deposition rate) is the deposition rate of the thin film formed by adding the diffusion improving material when the above-mentioned process is carried out. Here, the deposition rate (DR) is the value measured by using an ellipsometer device under conditions of room temperature and normal pressure for a thin film with a thickness of 3 to 30 nm, and the unit is Å / cycle.)

[0281] *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.

[0282] [Formula 2]

[0283] TIFF2025510866000024.tif9147

[0284] * SIMS (Secondary-ion mass spectrometry) C impurity: The C impurity value in the SIMS graph was confirmed by taking into consideration the C impurity content (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.

[0285] * Step coverage (%): The thin films deposited on a substrate having a complex structure with an aspect ratio of 22:1 according to Examples 1 to 3 and Comparative Examples 1 to 2 were horizontally cut at a position 100 nm from the top to the bottom (left figure) and at a position 100 nm from the bottom to the top (right figure). The step coverage was measured using a transmission electron microscope (TEM) and calculated according to the following Equation 3.

[0286] [Formula 3]

[0287] TIFF2025510866000025.tif10164

[0288] Specifically, a deposition process was performed under conditions for applying a diffusion-improving material to a substrate with a complex structure with an aspect ratio of 22:1, with an upper diameter of 90 nm, a lower diameter of 65 nm, and a via hole depth of about 2000 nm. In order to check the uniformity of the thickness deposited inside the vertically formed via hole and the step coverage, specimens were prepared by cutting horizontally at a position 100 nm from the top to the bottom and at a position 100 nm from the bottom to the top. The results were measured using a transmission electron microscope (TEM) and are shown in Table 1 below and Figures 3 to 5 below.

[0289] [Table 1]

[0290] As shown in Table 1, it was confirmed that in Examples 1 to 3, in which the thin film modifying composition according to the present invention was used, the deposition rate reduction rate and uniformity were significantly improved compared to Comparative Example 1, in which the thin film modifying composition according to the present invention was not used. Also, it was confirmed that in Examples 1 to 3, in which the thin film modifying composition according to the present invention was used, the deposition rate reduction rate was equal or similar to that of Comparative Example 2, in which a different type not considered to be a suitable type was used, and the uniformity was excellent.

[0291] In particular, it was confirmed that Examples 1 to 3, which used the thin film modifying composition according to the present invention, had a uniformity that was 20% or more better than Comparative Example 1, which did not use the composition, and Comparative Example 2, which used a shielding material alone (see Figure 2 below).

[0292] Furthermore, as shown in Figures 3 to 5 below, in Examples 1 to 3 in which the thin film modifying composition of the present invention was used, the step coverage was 99.1 to 100.2%, which was significantly improved compared to 95.0% in Comparative Example 1 in which the composition was not used.

Claims

1. The present invention includes 50 to 99 parts by weight of a shielding material having one or more unshared electron pairs selected from oxygen (O), sulfur (S), and phosphorus (P), and 1 to 50 parts by weight of a diffusion improving material, The thin film modifying composition is characterized in that the diffusion improving material has a boiling point in the range of 5 to 200°C.

2. The thin film modifying composition according to claim 1, wherein the shielding material is a compound represented by the following chemical formulas 1 and 2: [Chemical formula 1] 【Chemistry 1】 [Chemical formula 2] 【Chemistry 2】 (In the above Chemical Formulas 1 and 2, the R′ and R ” each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; The A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH, or -CH ２ and The B is —OH, —OCH ３ , -OCH ２ CH ３ , -CH ２ CH ３ , -SH, -SCH ３ , or -SCH ２ CH ３ and m is an integer from 0 to 3.

3. The thin film modifying composition according to claim 1, wherein the shielding material comprises at least one compound selected from the group consisting of compounds represented by the following formulas 1-1 to 1-4 and 2-1 to 2-4: [Chemical formulas 1-1 to 1-4] 【Chemistry 3】 [Chemical formulas 2-1 to 2-4] 【Chemistry 4】

4. The thin film modifying composition according to claim 1, wherein the diffusion improving material is at least one selected from the group consisting of octane, diethyl ether, methylene chloride, toluene, hexane, and ethanol.

5. The thin film is formed from one or more precursor compounds 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, which controls the reaction surface of the thin film formed from the precursor compound.

6. A method for forming a thin film, comprising: injecting a thin film modifying composition into a chamber, the composition including 50 to 99 parts by weight of a shielding material having one or more unshared electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P) and 1 to 50 parts by weight of a diffusion improving material, to shield a surface of a substrate that has been loaded, the diffusion improving material having a boiling point in the range of 5 to 200°C.

7. 7. The method of claim 6, 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.

8. 7. The method of claim 6, 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.

9. A semiconductor substrate comprising a thin film produced by the thin film formation method according to claim 6.

10. 10. The semiconductor substrate according to claim 9, wherein the thin film has a multi-layer structure of two or more layers.

11. A semiconductor device comprising the semiconductor substrate of claim 10.

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