Thin film modifying composition, thin film forming method using same, semiconductor substrate manufactured by method, and semiconductor device

Abstract

The present invention relates to a composition for modifying a thin film, a method for forming a thin film using the same, a semiconductor substrate manufactured by the method, and a semiconductor device, in which the composition for modifying a thin film uses both a masking material and a diffusion improving material to improve the reaction speed and appropriately reduce the growth rate of a thin film, thereby improving the yield of the thin film. According to the present invention, even if a thin film is formed on a substrate having a complicated structure under a high temperature condition, step coverage and thickness uniformity of the thin film can be greatly improved, and impurities are reduced, thereby having an effect of improving film quality.

Description

Technical Field

[0001] The present invention relates to a thin film modification composition, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured by the method, and more particularly to a thin film modification composition, a thin film forming method using the same, and a semiconductor substrate manufactured thereby, wherein by providing a thin film modification composition composed of a shielding substance and a diffusion improving substance, the substrate can be effectively shielded even under high temperature conditions to improve the reaction speed and appropriately reduce the thin film growth rate, so that even if a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved, and impurities can be greatly reduced to improve the film quality. Background Art

[0002] As the integration of memory and non-memory semiconductor devices increases, the fine structure of the substrate becomes increasingly complex.

[0003] As an example, the ratio of the width to the depth of the fine structure (hereinafter also referred to as the "aspect ratio") increases to above 20:1 or above 100:1. The larger the aspect ratio, the more difficult it is to form a deposition layer of uniform thickness along the surface of the complex fine structure.

[0004] Therefore, the step coverage (step coverage) that defines the thickness ratio of the deposited layers formed on the upper and lower parts in the depth direction of the fine structure has remained at around 90%, making it increasingly difficult to express the electrical characteristics of the component, and therefore its importance is gradually increasing. The above step coverage of 100% means that the thickness of the deposited layers formed on the upper and lower parts of the fine structure is the same, so it is necessary to develop a technology that makes the step coverage as close to 100% as possible.

[0005] That is, in order to obtain excellent and uniform physical properties of the thin film deposited on the substrate, high step coverage of the thin film is essential. Therefore, an atomic layer deposition (ALD) process that utilizes surface reactions is used instead of a chemical vapor deposition (CVD) process that mainly utilizes gas phase reactions. However, it is still difficult to achieve 100% step coverage.

[0006] When the deposition temperature is increased for the purpose of achieving 100% step coverage, there are difficulties in step coverage. First, in the deposition process consisting of two components, the increase in deposition temperature will not only lead to a sharp increase in the film growth rate (GPC), but even if the ALD process is used and implemented at a temperature of 300°C in order to alleviate the increase in GPC caused by the increase in deposition temperature, the deposition temperature will increase during the process. Therefore, it cannot be considered a solution.

[0007] In addition, a high-temperature process is required to achieve a metal oxide film with excellent film quality in a semiconductor device. It has been reported that increasing the atomic layer deposition temperature to 400°C reduces the concentration of residual carbon and hydrogen in the film (see the paper J. Vac. Sci. Technol. A, 35 (2017) 01B130).

[0008] However, the higher the deposition temperature, the more difficult it is to ensure step coverage. First, in the deposition process consisting of both precursors and reactants, an increase in deposition temperature will lead to a sharp increase in GPC (film growth rate). In addition, it can be confirmed that even if a conventional shielding agent is used to alleviate the increase in GPC caused by the increase in deposition temperature, GPC will increase by about 10% at a temperature of 300°C. That is, when deposition is performed at a temperature above 360°C, it is difficult to expect the GPC reduction effect provided by the shielding agent in the prior art.

[0009] Therefore, it is necessary to develop a method for forming a thin film and a semiconductor substrate manufactured by the method, by which a thin film with a complex structure can be effectively formed even at a high temperature with a low amount of residual impurities and significantly improved step coverage and film thickness uniformity. Summary of the invention

[0010] Problem that the invention aims to solve

[0011] In order to solve the technical problems in the prior art as described above, the object of the present invention is to provide a thin film modification composition, a thin film forming method using the same, and a semiconductor substrate manufactured by the method, wherein the substrate is effectively shielded by using a shielding substance and a diffusion improving substance at the same time to improve the reaction rate, and the thin film growth rate is appropriately reduced, so that even if a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved, and impurities can be reduced to improve the film quality.

[0012] The object of the present invention is to improve the crystallinity and oxidation fraction of a thin film, thereby improving the density, electrical properties and dielectric properties of the thin film.

[0013] The above-mentioned object and other multiple objects of the present invention can be fully achieved by the present invention described below.

[0014] Means used to solve problems

[0015] In order to achieve the above-mentioned purpose, the present invention provides a thin film modification composition, which comprises: 50 to 99 parts by weight of a shielding substance containing one or more lone electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P); and 1 to 50 parts by weight of a diffusion improving substance, wherein the boiling point of the diffusion improving substance is in the range of 5 to 200°C.

[0016] The shielding material may include a linear or cyclic saturated or unsaturated hydrocarbon containing two or more oxygen (O), phosphorus (P) or sulfur (S) and having 3 to 15 carbon atoms.

[0017] The shielding substance 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 an oxygen atom by a double bond.

[0018] The shielding substance may include a compound having a structure in which one end of a central carbon atom double-bonded to an oxygen atom contains oxygen (O), phosphorus (P), or sulfur (S) and the other end contains carbon (C).

[0019] The shielding substance may be one or more selected from the group consisting of the compounds represented by the following Chemical Formula 1 to the compounds represented by the following Chemical Formula 2.

[0020] [Chemical formula 1]

[0021]

[0022] [Chemical formula 2]

[0023]

[0024] (In the above Chemical Formulae 1 to 2, R' and R" are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms,

[0025] A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH or -CH2,

[0026] The above B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3 or -SCH2CH3, and m is an integer of 0 to 3.)

[0027] The shielding material may include one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulae 1-1 to 1-4 and Chemical Formulae 2-1 to 2-4.

[0028] [Chemical Formula 1-1] to [Chemical Formula 1-4]

[0029]

[0030] [Chemical Formula 2-1] to [Chemical Formula 2-4]

[0031]

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

[0033] The boiling point of the diffusion improving substance may be 5 to 200°C, and as a specific example, may be 10 to 150°C, and preferably within the range of 25 to 140°C.

[0034] The diffusion improving substance is preferably in liquid form at room temperature in order to improve the diffusibility and uniformity of the shielding substance.

[0035] The diffusion improving substance may be at least one selected from octane, ether, dichloromethane, toluene, hexane and ethanol.

[0036] The refractive index of the diffusion improving substance may be 1.30 or more, 1.30 to 1.70, 1.35 to 1.60, or 1.36 to 1.50.

[0037] The deposition rate reduction rate of the thin film modifying composition represented by the following Mathematical Formula 1 may be 30% or more.

[0038] [Mathematical formula 1]

[0039] Deposition rate (DR) reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0040] (In this formula, DR (Deposition rate), ) is the rate of film deposition. When depositing a film formed from a precursor and a reactant, DR i Initial deposition rate is the deposition rate of a thin film without adding diffusion-improving substances. f The final deposition rate is the deposition rate of the thin film formed by adding the diffusion-improving material during the above process. The deposition rate (DR) is the value of the film with a thickness of 3 to 30 nm measured by an ellipsometer under normal temperature and pressure conditions. The unit used is )

[0041] The above-mentioned thin film can be a stacked film of one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd.

[0042] The above-mentioned thin film can be used as an anti-diffusion film, an etching stopper film, an electrode film, a dielectric film, a gate insulating film, a blocking oxide film, or a charge trap.

[0043] In addition, the present invention provides a thin film forming method, which includes the following steps: injecting a thin film modification composition into a chamber to mask the surface of a loaded substrate; the thin film modification composition comprises: 50 to 99 parts by weight of a masking substance containing one or more lone electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P), and 1 to 50 parts by weight of a diffusion improving substance; wherein the diffusion improving substance is one or more selected from 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.

[0044] The precursor compound used in the above-mentioned thin film forming method may be a compound represented by Chemical Formula 3 below.

[0045] [Chemical formula 3]

[0046]

[0047] In the above chemical formula 3, M is one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd, and L 1 , L 2 , L 3 and L 4 is -H, -X, -R, -OR, -NR2 or Cp(cyclopentadienyl)2, which may be the same or different, wherein -X is F, Cl, Br or I, and -R is C1-C10 alkyl, C1-C10 alkenyl or C1-C10 alkynyl, which may be linear or cyclic, and the above L 1 , L 2 , L 3 and L 4 The number of the ions may be 2 to 6 depending on the oxidation valence of the central metal.

[0048] For example, when the central metal is divalent, L 1 and L 2 It can act as a ligand to bind to the central metal. When the central metal is hexavalent, L 1, L 2 , L 3 , L 4 , L 5 , L 6 Can be combined with the central metal, equivalent to L 1 To L 6 The ligands may be the same as or different from each other.

[0049] In the above chemical formula 3, L 1 , L 2 , L 3 and L 4 is -H, -X or -R, which may be the same as or different from each other, wherein -R is a C1-C10 alkyl, a C1-C10 alkenyl or a C1-C10 alkynyl, which may be linear or cyclic.

[0050] In the above chemical formula 3, L 1 , L 2 , L 3 and L 4 It is -H, -OR, -NR2 or Cp(cyclopentadienyl)2, which may be the same as or different from each other, wherein -R may be H, C1~C10 alkyl, C1~C10 alkenyl, C1~C10 alkynyl, iPr or tBu.

[0051] In the above chemical formula 3, L 1 , L 2 , L 3 and L 4 is -H or -X, which may be the same as or different from each other, wherein -X may be F, Cl, Br or I.

[0052] In addition, the present invention provides a thin film forming method, which includes: step i), vaporizing the above-mentioned thin film modification composition to shield the substrate loaded in the chamber; step ii), using a purge gas to perform a first purge on the inside of the above-mentioned chamber; step iii), vaporizing the precursor compound and adsorbing it in an area away from the above-mentioned shielding area; step iv), using a purge gas to perform a second purge on the inside of the above-mentioned chamber; step v), supplying a reaction gas to the inside of the above-mentioned chamber; and step vi), using a purge gas to perform a third purge on the inside of the above-mentioned chamber.

[0053] The above-mentioned precursor compound, as a molecule formed by one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd, can be a precursor having a vapor pressure greater than 0.01mTorr and less than or equal to 100Torr under a temperature condition of 25°C.

[0054] 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.

[0055] The thin film forming method may include the following steps: after vaporizing and injecting the thin film modifying composition or precursor compound, performing plasma post-treatment.

[0056] The amount of the purge gas introduced into the chamber in the above step ii) and the above step iv) may be 10 to 100,000 times the volume of the film modifying composition introduced.

[0057] The above-mentioned reaction gas is an oxidant, a nitriding agent or a reducing agent. The above-mentioned reaction gas, the film modification composition and the precursor compound can be delivered into the chamber via a vapor flow control (VFC) method, a direct liquid injection (DLI) method or a liquid delivery system (LDS) method.

[0058] The above-mentioned thin film can 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.

[0059] The substrate loaded in the chamber is heated to 100° C. to 800° C., and the ratio of the amount (mg / cycle) of the thin film modification composition to the amount of the precursor compound loaded into the chamber may be 1:1 to 1:20.

[0060] In addition, the present invention provides a semiconductor substrate produced by the above-mentioned thin film forming method.

[0061] The above-mentioned film can be a multi-layer structure of two layers or three layers or more.

[0062] In addition, the present invention provides a semiconductor device, which includes the semiconductor substrate mentioned above.

[0063] The semiconductor substrate may 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.

[0064] Effects of the Invention

[0065] According to the present invention, a film modification composition is provided, which can effectively shield adsorption on the substrate surface to improve the reaction rate and appropriately reduce the film growth rate, thereby improving step coverage even when forming a film on a substrate with a complex structure under high temperature conditions.

[0066] In addition, when forming a thin film, process byproducts are more effectively reduced to prevent corrosion and degradation, and the film quality is improved to improve the crystallinity of the thin film, thereby improving the electrical properties of the thin film.

[0067] In addition, the step coverage and density of the thin film can be improved. Furthermore, a thin film forming method using the thin film modifying composition and a semiconductor substrate manufactured by the method are provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 This is a diagram schematically showing the deposition process sequence of the present invention mainly in one cycle.

[0069] Figure 2 This is a diagram comparing the calculated unevenness of each thin film obtained in Examples 1 and 2 and Comparative Examples 2 and 3 described later.

[0070] Figures 3 to 5 These are TEM photographs of the step coverage measured at the upper and lower ends of each of the thin films obtained in Examples 1 to 3 described later. DETAILED DESCRIPTION

[0071] Hereinafter, the thin film modifying composition of the present invention, the thin film forming method using the same, and the semiconductor substrate produced by the method will be described in detail.

[0072] In the present invention, unless otherwise defined, the term "shielding" means not only reducing, preventing or blocking the adsorption of precursor compounds for forming a thin film onto a substrate, but also reducing, preventing or blocking the adsorption of process byproducts onto a substrate.

[0073] In the present invention, unless otherwise defined, the term "diffusion improving" means a substance that helps the diffusion of a shielding substance to improve uniformity.

[0074] The inventors of the present invention have confirmed that the use of a shielding substance (capable of shielding the adsorption of a precursor compound used to form a thin film on the surface of a substrate loaded inside a chamber) and a diffusion improving substance (capable of modifying the uniformity of the generated thin film) can improve the reaction rate under high temperature conditions, and even if applied to a substrate with a complex structure, the uniformity of the thin film can be ensured by improving the film quality, thereby greatly improving the step coverage, especially, it can be deposited at a thinner thickness, and the amount of O, Si, metal, metal oxides and residual carbon that have been difficult to reduce as process byproducts can be improved. Based on this, the thin film modification composition was studied, and the present invention was completed.

[0075] As an example, the above-mentioned thin film can be provided by one or more precursors 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, and can provide an oxide film, a nitride film or a metal film. At this time, the effect to be achieved by the present invention can be fully obtained.

[0076] As a specific example, the thin film may have a film composition of 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.

[0077] The thin film further contains SiH and SiOH in the above film composition.

[0078] The above-mentioned thin film can be used not only as a common anti-diffusion film, but also can be applied to semiconductor devices as an etching stopper film, an electrode film, a dielectric film, a gate insulating film, a blocking oxide film or a charge trap.

[0079] In the present invention, the precursor compound used to form the thin film is a molecule with 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 as the central metal atom (M) and having one or more ligands composed of C, N, O, H, X (halogen). When it is a precursor with a vapor pressure of 1mTorr to 100Torr at a temperature of 25°C, it can maximize the film quality improvement effect described later.

[0080] As an example, the precursor compound may be a compound represented by the following Chemical Formula 3.

[0081] [Chemical formula 3]

[0082]

[0083] (In the above chemical formula 3, M is one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd, L 1 , L 2 , L 3 and L 4 is -H, -X, -R, -OR, -NR2 or Cp(cyclopentadienyl)2, which may be the same or different, wherein -X is F, Cl, Br or I, and -R is a C1-C10 alkyl, a C1-C10 alkenyl or a C1-C10 alkynyl, which may be linear or cyclic.

[0084] In the above chemical formula 3, the above M is hafnium (Hf), silicon (Si), zirconium (Zr) or aluminum (Al), preferably hafnium (Hf) or silicon (Si). In this case, the process by-product reduction effect is significant, the step coverage is excellent, and it has the advantages of improving the film density, and the electrical properties, insulation and dielectric properties of the film are better.

[0085] The above L 1 , L 2 , L 3 and L 4 is -H, -X or -R, which may be the same as or different from each other, wherein -R is a C1-C10 alkyl, a C1-C10 alkenyl or a C1-C10 alkynyl, and may be in a linear or cyclic structure.

[0086] In addition, the above L 1 , L 2 , L 3 and L 4 It is -H, -OR, -NR2 or Cp(cyclopentadienyl)2, which may be the same as or different from each other, wherein -R may be H, C1~C10 alkyl, C1~C10 alkenyl, C1~C10 alkynyl, iPr or tBu.

[0087] In addition, in the above chemical formula 3, L 1 , L 2 , L 3 and L 4 is -H or -X, which may be the same as or different from each other, wherein -X may be F, Cl, Br or I.

[0088] Specifically, the silicon precursor compound can be selected from SiH4, SiHCl3, SiH2Cl2, SiCl4, Si2Cl6, Si3Cl8, Si4Cl 10, SiH2[NH(C4H9)]2, Si2(NHC2H5)4, Si3NH4(CH3)3, SiH3[N(CH3)2], SiH2[N(CH3)2]2, SiH[N(CH3)2]3, Si[N(CH3)2]4.

[0089] In addition, hafnium precursor compounds such as tris(dimethylamido)cyclopentadienylhafnium (CpHf(NMe2)3) and (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium (Cp(CH2)3NM3Hf(NMe2)2) can be used.

[0090] In addition, the aluminum precursor compound may be, for example, trimethyl aluminum (TMA), tris(dimethylamido)aluminum (TDMAA), or aluminum chloride (AlCl 3 ).

[0091] The above-mentioned film modifying composition may be composed of a shielding substance and a diffusion improving substance.

[0092] Among them, the shielding material can include a compound containing one or more lone electron pairs selected from oxygen (O), sulfur (S) and phosphorus (P), preferably a linear or cyclic saturated hydrocarbon or unsaturated hydrocarbon containing two or more selected from nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) and having a carbon number of 3 to 15. At this time, when forming a thin film, a shielding area that will not remain in the thin film can be formed, and side reactions can be suppressed while forming a relatively sparse thin film. The film growth rate can be adjusted to reduce process by-products in the thin film, thereby reducing corrosion and deterioration, and improving the crystallinity of the thin film. When a metal oxide film is formed, a stoichiometric oxidation state is reached. Even if a thin film is formed on a substrate with a complex structure under high temperature conditions, the step coverage and thickness uniformity of the thin film can be greatly improved.

[0093] As a specific example, the above-mentioned shielding material is a compound having a structure containing oxygen (O), phosphorus (P) or sulfur (S) at both ends of a central carbon atom double-bonded to an oxygen atom. Therefore, the process by-product reduction effect is significant, the step coverage is excellent, and the film density improvement effect and the electrical properties of the film are more outstanding.

[0094] Unless otherwise specified, the above structures containing oxygen (O), phosphorus (P) or sulfur (S) at both ends of the central carbon atom connected to the oxygen atom by double bonds refer to

[0095] As a specific example, the above-mentioned shielding material has a structure in which one end of a central carbon atom connected to an oxygen atom by a double bond contains oxygen (O), phosphorus (P) or sulfur (S) and the other end contains carbon (C). Therefore, the process by-product reduction effect is significant, the step coverage is excellent, and the film density improvement effect and the electrical properties of the film are more outstanding.

[0096] Unless otherwise specified, the structure in which one end of the central carbon atom connected to an oxygen atom by a double bond contains oxygen (O), phosphorus (P) or sulfur (S) and the other end contains carbon (C) refers to

[0097] As a specific example, the above-mentioned masking material can be one or more compounds selected from the following chemical formulas 1 to 2. In this case, when forming a thin film, a masking area that will not remain in the thin film can be formed, and side reactions can be suppressed while forming a relatively sparse thin film. The film growth rate can also be adjusted to reduce process by-products in the thin film, thereby reducing corrosion and degradation, and improving the crystallinity of the thin film. Even if a thin film is formed on a substrate with a complex structure, the step coverage and thickness uniformity of the thin film can be greatly improved.

[0098] [Chemical formula 1]

[0099]

[0100] [Chemical formula 2]

[0101]

[0102] (In the above Chemical Formulae 1 to 2, R' and R" are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms,

[0103] A is oxygen (O), sulfur (S), phosphorus (P), nitrogen (N), -CH or -CH2,

[0104] The above B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3 or -SCH2CH3, and m is an integer of 0 to 3.)

[0105] In the above chemical formula 1, the above A is oxygen (O) or sulfur (S), preferably oxygen (O). In this case, the process by-product reduction effect is significant, the step coverage is excellent, and it has the advantages of improving the film density, and the electrical properties, insulation and dielectric properties of the film are better.

[0106] The above R' is an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. In this case, the process by-product reduction effect is significant, the step coverage is excellent, and there are advantages such as improved film density, better electrical properties, insulation and dielectric properties of the film.

[0107] The above m is an integer of 1 to 2, and preferably an integer of 1.

[0108] In the above chemical formula 2, the above B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3 or -SCH2CH3. At this time, the effect of reducing process by-products is significant, the step coverage is excellent, and it has the advantages of improving the film density and better electrical properties of the film.

[0109] The above R" is an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. In this case, the process by-product reduction effect is significant, the step coverage is excellent, and there are advantages of improving the film density and the electrical properties of the film are more outstanding.

[0110] As an example, when the shielding substance is 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. As a specific example, it may be a compound having a refractive index in the range of 1.4 to 1.48, and preferably a compound having a refractive index in the range of 1.4 to 1.46.

[0111] As an example, when the shielding substance is 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. As a specific example, it may be a compound having a refractive index in the range of 1.33 to 1.39, and preferably a compound having a refractive index in the range of 1.35 to 1.39.

[0112] At this time, on the substrate, based on the difference in adsorption distribution of the shielding agent having the above-mentioned structure, a deposition layer with uniform thickness is formed as a shielding area that will not remain in the film, so as to reduce the deposition rate of the film and appropriately reduce the growth rate of the film. Therefore, even when a thin film is formed on a substrate with a complex structure under high temperature conditions, the step coverage and the thickness uniformity of the film can be greatly improved, and the adsorption of film precursors and process by-products can be prevented to effectively protect the surface of the substrate and effectively remove process by-products.

[0113] In particular, while forming a relatively sparse film, the growth rate of the formed film is greatly reduced. Therefore, even if applied to a substrate with a complex structure, the uniformity of the film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of O, Si, metals, metal oxides remaining as process by-products, and residual carbon that was previously difficult to reduce.

[0114] The above-mentioned shielding material 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. At this time, a thin film shielding area is provided, which not only has a significant effect on adjusting the growth rate of the thin film, but also has a significant effect on removing process by-products, and has excellent effects on improving step coverage and film quality, and the uniformity of the generated thin film is significantly improved.

[0115] [Chemical Formula 1-1] to [Chemical Formula 1-4]

[0116]

[0117] [Chemical Formula 2-1] to [Chemical Formula 2-4]

[0118]

[0119] The boiling point of the above-mentioned diffusion improving substance is in the range of 5-200°C, 5-190°C or 6-190°C. At this time, the diffusivity of the above-mentioned shielding substance is improved, and when forming a thin film, side reactions are suppressed and the growth rate of the thin film is adjusted to reduce process by-products in the thin film, thereby reducing corrosion or deterioration. Not only is the film quality improved, such as the improvement of the crystallinity of the thin film, but also when a metal oxide film is formed, a stoichiometric oxidation state is reached. Even if a thin film is formed on a substrate with a complex structure under high temperature conditions, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0120] As an example, the solubility of the diffusion improving substance in water (25°C) is less than 200 mg / L, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, it has the advantages of low reactivity to precursor compounds and easy water management.

[0121] In the present invention, the solubility may be based on the measurement method and standard conventionally used in the art. As an example, the solubility may be measured by HPLC method for a saturated solution.

[0122] The above-mentioned diffusion improving substance is preferably one or more selected from octane, ether and dichloromethane. The deposition rate reduction rate represented by mathematical formula 1 can be 30% or more. As a specific example, it can be 40% or more, preferably 50% or more. At this time, based on the difference in adsorption distribution of the shielding agent having the above-mentioned structure, a deposition layer with uniform thickness is formed as a shielding area that will not remain in the film, so that while forming a relatively sparse film, the growth rate of the formed film is greatly reduced. Therefore, even if applied to a substrate with a complex structure, the uniformity of the film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of O, Si, metals, metal oxides and residual carbon that remain as process by-products that were previously difficult to reduce.

[0123] [Mathematical formula 1]

[0124] Deposition rate (DR) reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0125] (In this formula, DR (Deposition rate), ) is the rate of film deposition. When depositing a film formed from a precursor and a reactant, DR i Initial deposition rate is the deposition rate of a thin film without adding diffusion-improving substances. f The final deposition rate is the deposition rate of the thin film formed by adding the diffusion-improving material during the above process. The deposition rate (DR) is the value of the film with a thickness of 3 to 30 nm measured by an ellipsometer under normal temperature and pressure conditions. The unit used is )

[0126] In the above mathematical formula 1, the film growth rate per cycle represents the film deposition thickness per cycle when the film modifying composition is used or not used. That is, the deposition rate may be, for example, an average deposition rate obtained by measuring the final thickness of a thin film having a thickness of 3 to 30 nm using an ellipsometer under normal temperature and pressure conditions and dividing the result by the total number of cycles.

[0127] In the above mathematical formula 1, "when a film modifying composition is not used" means a case where a film is manufactured by adsorbing only a precursor compound on a substrate in a film deposition process. As a specific example, it means a case where a film is formed by omitting the step of adsorbing a film modifying composition and the step of purging the non-adsorbed film modifying composition in the above-mentioned film forming method.

[0128] As an example, the diffusion improving substance may be a compound having a refractive index of 1.30 or more, 1.30 to 1.70, 1.35 to 1.60, or 1.36 to 1.50.

[0129] At this time, the precursor compound is properly shielded from adsorption on the substrate, thereby improving the reaction rate. Even if a thin film is formed on a substrate with a complex structure, the step coverage and thickness uniformity of the thin film can be greatly improved, and the adsorption of thin film precursors and process by-products can be prevented to effectively protect the surface of the substrate and effectively remove process by-products.

[0130] The weight ratio of the masking substance to the diffusion improving substance contained in the film modification composition can be 50:50 to 99:1, a smaller range of 60:40 to 95:5, preferably 70:30 to 92:8, and more preferably 80:20 to 90:10. At this time, while forming a relatively sparse film, the growth rate of the formed film is greatly reduced. Therefore, even if applied to a substrate with a complex structure, the uniformity of the film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness, and the amount of O, Si, metal, metal oxides and residual carbon that are difficult to reduce as process byproducts can be improved.

[0131] For reference, the diffusion improving substance may be, for example, octane having a boiling point of about 125.6° C., dichloromethane having a boiling point of about 39.6° C., or ether having a boiling point of about 34.6° C.

[0132] The deposition rate reduction rate of the thin film modifying composition represented by the following Mathematical Formula 1 may be 30% or more.

[0133] [Mathematical formula 1]

[0134] Deposition rate (DR) reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0135] (In this formula, DR (Deposition rate), ) is the rate of film deposition. When depositing a film formed from a precursor and a reactant, DR i Initial deposition rate is the deposition rate of a thin film without adding diffusion-improving substances. f The final deposition rate is the deposition rate of the thin film formed by adding the diffusion-improving material during the above process. The deposition rate (DR) is the value of the film with a thickness of 3 to 30 nm measured by an ellipsometer under normal temperature and pressure conditions. The unit used is )

[0136] The film shielding region does not remain on the film.

[0137] At this time, unless otherwise specifically defined, no residue means that when the components are analyzed by XPS, the C element is 0.1 atom %, the Si element is less than 0.1 atom %, the N element is less than 0.1 atom %, and the halogen element is less than 0.1 atom %. More preferably, in a secondary ion mass spectrometry (SIMS) measurement method or an X-ray photoelectron spectroscopy (XPS) measurement method that measures by digging into the substrate in the depth direction, when considering the increase or decrease rate of C, N, Si, and halogen impurities before and after using a shielding agent under the same deposition conditions, the signal intensity increase or decrease rate of each element species is preferably less than 5%.

[0138] As an example, in the above-mentioned thin film forming method, when the above-mentioned thin film modification composition is used, the non-uniformity represented by the following mathematical formula 2 can be less than 1.2%. As a specific example, it can be less than 1.1%, preferably 0.01% to 1.1%. At this time, based on the difference in adsorption distribution of the shielding agent having the above-mentioned structure, a deposition layer with uniform thickness is formed as a replacement area that will not remain in the thin film, so that while forming a relatively sparse thin film, the growth rate of the formed thin film is greatly reduced. Therefore, even if applied to a substrate with a complex structure, the uniformity of the thin film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of O, Si, metals, metal oxides and residual carbon that remain as process by-products and have been difficult to reduce in the past.

[0139] [Mathematical formula 2]

[0140] Unevenness % = [{(maximum thickness - minimum thickness) / 2}×average thickness]×100

[0141] The maximum thickness and the minimum thickness are respectively selected by measuring the thin film using the ellipsometer used when measuring the above-mentioned deposition rate reduction rate.

[0142] As an example, the thickness is selected by measuring the thickness at 10 arbitrary locations, preferably by measuring the thickness at four edge locations in the east, west, south, and north directions and one center location of a 300 mm wafer.

[0143] As an example, the content of the halogen compound in the above-mentioned film can be less than 100 ppm. For reference, when too much halogen remains, when a nitriding agent is used under the temperature condition of 200 to 300° C. as an experimental condition described later, by-products including NH4Cl are generated and remain in the film, so it is not preferred.

[0144] The above-mentioned thin film may be used as an etching stopper film, an electrode film, a dielectric film, a gate insulating film, a blocking oxide film, or a charge trap, but is not limited thereto.

[0145] Preferably, the above-mentioned film modification composition can be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, impurities may remain in the film or cause side reactions with precursors or reactants. Therefore, substances with a purity of 99% or more should be used as much as possible.

[0146] Preferably, the thin film modification composition is used in an atomic layer deposition (ALD) process. In this case, the thin film modification composition can effectively protect the surface of the substrate without hindering the adsorption of the precursor compound, and has the advantage of effectively removing process byproducts.

[0147] Preferably, the density of the film modification composition can be 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20°C) can be 0.1-300 mmHg or 1-300 mmHg. Within this range, it has excellent effects of improving step coverage, uniformity of film thickness and film quality.

[0148] More preferably, the density of the film modification composition may be 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, it has excellent effects on improving step coverage, film thickness uniformity and film quality.

[0149] In particular, while forming a relatively sparse film, the growth rate of the formed film is greatly reduced. Therefore, even if applied to a substrate with a complex structure, the uniformity of the film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of O, Si, metals, metal oxides remaining as process by-products, and residual carbon that was previously difficult to reduce.

[0150] The thin film forming method of the present invention comprises the following steps: injecting the above-mentioned thin film modification composition into a chamber to replace the ligand of the precursor compound adsorbed on the surface of the loaded substrate; at this time, the ligand of the precursor adsorbed on the substrate can be effectively replaced to improve the reaction rate and appropriately reduce the thin film growth rate, so that even if a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0151] In the step of masking the surface of the substrate with the above-mentioned thin film modification composition, the feeding time (Feeding Time, sec) of the thin film modification composition to the substrate surface per cycle is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, more preferably 0.04 to 6 seconds, and further preferably 0.05 to 5 seconds. Within this range, the film has the advantages of low growth rate and excellent step coverage and economy.

[0152] In the present invention, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle when the volume of the chamber is 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle when the volume of the chamber is 18 L.

[0153] As a preferred embodiment, the above-mentioned thin film forming method may include: step i), vaporizing the above-mentioned thin film modification composition to shield the surface of the substrate loaded in the chamber; step ii), using a purge gas to purge the interior of the above-mentioned chamber for the first time; step iii), vaporizing the precursor compound and adsorbing it in an area away from the above-mentioned shielding area; step iv), using a purge gas to purge the interior of the above-mentioned chamber for the second time; step v), supplying a reaction gas to the interior of the above-mentioned chamber; and step vi), using a purge gas to purge the interior of the above-mentioned chamber for the third time. At this time, the above-mentioned steps i) to vi) can be used as a unit cycle, and the above cycle can be repeatedly implemented until a thin film of a desired thickness is obtained (refer to Figure 1), and when the thin film modification composition of the present invention is added before the precursor compound in a cycle to improve the film quality in this way, even if deposition is carried out at a high temperature, the film growth rate can be appropriately reduced, and the generated process by-products can be effectively removed to reduce the resistivity of the film and significantly improve the step coverage.

[0154] As a preferred example, in the thin film forming method of the present invention, the thin film modification composition of the present invention can be added before the precursor compound in one cycle to allow it to be adsorbed on the substrate. At this time, even if the thin film is deposited at a high temperature, the film growth rate can be appropriately reduced, thereby greatly reducing process by-products and greatly improving step coverage. The crystallinity of the thin film is increased to reduce the resistivity of the thin film, and even if it is applied to semiconductor devices with a large aspect ratio, the thickness uniformity of the thin film can be greatly improved to ensure the reliability of the semiconductor device.

[0155] As an example, in the above-mentioned thin film forming method, when the above-mentioned thin film modification composition is deposited before or after the deposition of the precursor compound, the number of repetitions of the unit cycle can be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, as needed. Within this range, the desired film thickness can be obtained and the effect to be achieved by the present invention can be fully achieved.

[0156] As an example, in the present invention, the above-mentioned chamber can 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.

[0157] In the present invention, the thin film forming method may include the following steps: after vaporizing and injecting the thin film modifying composition or precursor compound, plasma post-treatment is performed, which can improve the growth rate of the thin film and reduce process byproducts.

[0158] When the thin film modification composition is injected onto the substrate and the precursor compound is adsorbed, the amount of the purge gas introduced into the chamber in the step of purging the non-adsorbed thin film modification composition is sufficient to remove the non-adsorbed thin film modification composition. For example, it can be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the non-adsorbed thin film modification composition can be sufficiently removed, thereby forming a uniform thin film and preventing the deterioration of the film quality. The amounts of the purge gas and the thin film modification composition introduced are based on one cycle, respectively, and the volume of the thin film modification composition represents the volume of the vaporized thin film modification composition vapor.

[0159] As a specific example, when the above-mentioned film modification composition is injected (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and in the step of purging the unadsorbed film modification composition, the purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec, the injection amount of the purge gas is 602 times the injection amount of the film modification composition.

[0160] In the step of purging the unadsorbed precursor compound, the amount of the purge gas introduced into the chamber can be sufficient to remove the unadsorbed precursor compound. For example, it can be 10 to 100,000 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. Within this range, the unadsorbed precursor compound can be sufficiently removed to form a uniform thin film and prevent the degradation of the film quality. The amounts of the purge gas and the precursor compound introduced are based on one cycle, respectively, and the volume of the precursor compound represents the volume of the vaporized precursor compound vapor.

[0161] In addition, in the purge step performed immediately after the reaction gas supply step, as an example, the amount of the purge gas introduced into the chamber may be 10 to 100,000 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. Within this range, the desired effect can be fully obtained. The amounts of the purge gas and the reaction gas introduced are based on one cycle, respectively.

[0162] Preferably, the film modification composition and the precursor compound can be delivered into the chamber by VFC, DLI or LDS, and more preferably, can be delivered into the chamber by LDS.

[0163] As an example, the substrate loaded in the chamber can be heated to 50-400°C. As a specific example, it can be heated to 50-400°C. The film modification composition or precursor compound can be injected into the substrate in an unheated or heated state. According to the deposition efficiency, it is also possible to heat it during the deposition process after injecting it in an unheated state. As an example, it can be injected into the substrate at 50-400°C within 1-20 seconds.

[0164] The ratio of the amount (mg / cycle) of the above-mentioned film modification composition to the above-mentioned precursor compound added into the chamber is preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, more preferably 1:2 to 1:12, and further preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and reducing process by-products is significant.

[0165] The above-mentioned precursor materials can be used in combination with a non-polar solvent.

[0166] The above-mentioned non-polar solvent can use an alkane or cycloalkane with a carbon number of 1 to 5. Specifically, it can contain 5 weight % to 95 weight % relative to the total weight of the precursor compound and the non-polar solvent, more preferably 10 weight % to 90 weight %, even more preferably 40 weight % to 90 weight %, and most preferably 70 weight % to 90 weight %.

[0167] Even if the above-mentioned type of non-polar solvent is used, when the amount of the non-polar solvent used is greater than the above-mentioned upper limit value, impurities will be induced, thereby causing an increase in the impurity values ​​in the resistor and the film. When the content of the above-mentioned organic solvent is less than the above-mentioned lower limit value, there are the disadvantages that the effect of improving the step coverage by adding the solvent and the effect of reducing impurities such as chloride (Cl) ions are not significant.

[0168] As an example, in the above-mentioned thin film forming method, when the above-mentioned thin film modifying composition is used, the deposition rate reduction rate represented by Mathematical Formula 1 can be 30% or more, and as a specific example, can be 35% or more. At this time, based on the difference in adsorption distribution of the shielding agent having the above-mentioned structure, a deposition layer with uniform thickness is formed as a replacement area that will not remain in the thin film, thereby forming a relatively sparse thin film while greatly reducing the growth rate of the formed thin film. Therefore, even if applied to a substrate with a complex structure, the uniformity of the thin film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of O, Si, metals, metal oxides and residual carbon that remain as process by-products and have been difficult to reduce in the past.

[0169] [Mathematical formula 1]

[0170] Deposition rate (DR) reduction rate = [{(DR i )-(DR f )} / (DR i )]×100

[0171] (In this formula, DR (Deposition rate), ) is the rate of film deposition. When depositing a film formed from a precursor and a reactant, DR i Initial deposition rate is the deposition rate of a thin film without adding diffusion-improving substances. fThe final deposition rate is the deposition rate of the thin film formed by adding the diffusion-improving material during the above process. The deposition rate (DR) is the value of the film with a thickness of 3 to 30 nm measured by an ellipsometer under normal temperature and pressure conditions. The unit used is )

[0172] The above-mentioned thin film forming method has a film thickness of The residual halogen intensity (c / s) in the film is preferably 100,000 or less, more preferably 70,000 or less, more preferably 50,000 or less, and further preferably 10,000 or less. As a preferred embodiment, it can be 5,000 or less, more preferably 1,000 to 4,000, and further preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and degradation is excellent.

[0173] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or a manner close thereto, which is advantageous in terms of film quality.

[0174] The above-mentioned ALD (atomic layer deposition process) is very beneficial for manufacturing integrated circuits (ICs) requiring high aspect ratios. In particular, it has advantages such as excellent step conformality, uniformity, and precise thickness control based on a self-limiting thin film growth mechanism.

[0175] As an example, the above-mentioned thin film forming method can be implemented at a deposition temperature in the range of 50°C to 800°C, preferably in the range of 100°C to 700°C, more preferably in the range of 200°C to 650°C, and even more preferably in the range of 220°C to 400°C. Within this range, it has the effect of realizing the characteristics of the ALD process and growing a thin film with excellent film quality.

[0176] As an example, the above-mentioned thin film forming method can be implemented 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, the effect of obtaining a thin film with uniform thickness can be achieved.

[0177] In the present invention, the deposition temperature and the deposition pressure may be measured by the temperature and pressure formed in the deposition chamber or by the temperature and pressure applied to the substrate in the deposition chamber.

[0178] Preferably, the above-mentioned thin film forming method may include the following steps: before the above-mentioned thin film modification composition is introduced into the chamber, the temperature in the chamber is increased to the deposition temperature; and / or before the above-mentioned thin film modification composition is introduced into the chamber, an inert gas is injected into the chamber for purging.

[0179] In addition, in the present invention, a thin film manufacturing apparatus capable of implementing the above-mentioned thin film manufacturing method may include: an ALD chamber; a first vaporizer for vaporizing a thin film modification composition; a first delivery unit for delivering the vaporized thin film modification composition into the ALD chamber; a second vaporizer for vaporizing a thin film precursor; and a second delivery unit for delivering the vaporized thin film precursor into the ALD chamber. The vaporizer and the delivery unit may be any vaporizer and delivery unit conventionally used in the art.

[0180] The first vaporizer for vaporizing the thin film modifying composition may be divided into at least two structures, namely, a vaporizer for vaporizing the shielding substance and a vaporizer for vaporizing the diffusion improving substance, as required.

[0181] The above-mentioned thin film forming method will be described as a specific example. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of performing atomic layer deposition.

[0182] The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0183] The substrate may further have a conductive layer or an insulating layer formed on an upper portion thereof.

[0184] The film modification composition and the precursor compound or a mixture thereof with a non-polar solvent are prepared respectively to deposit a film on a substrate placed in the deposition chamber.

[0185] Then, after the prepared film modifying composition (eg, masking material) is injected into the vaporizer, it is changed into a vapor phase to be transported to the deposition chamber and adsorbed on the substrate, and then purging is performed to remove the unadsorbed film modifying composition.

[0186] Next, after the prepared precursor compound or its mixture with a non-polar solvent (thin film forming composition) is injected into the vaporizer, it is changed into a vapor phase so that it can be transported to the deposition chamber and adsorbed on the substrate, masked with a pre-injected masking material, and then the unadsorbed precursor compound or its mixture with a non-polar solvent is purged.

[0187] In the present invention, as an example, the method of delivering the thin film modification composition and the precursor compound (thin film forming composition) to the deposition chamber can use a method of delivering volatile gas (Vapor Flow Control, VFC) using a gas phase flow control (Mass Flow Controller, MFC) method or a method of delivering liquid (Liquid Delivery System, LDS) using a liquid phase flow control (Liquid Mass Flow Controlle, LMFC) method. Preferably, the LDS method is used.

[0188] At this time, as a carrier gas or dilution gas for transporting the thin film modification composition and precursor compounds to the substrate, one or a mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited to this.

[0189] In the present invention, as an example, an inert gas may be used as the purge gas, and preferably, the above-mentioned carrier gas or diluent gas may be used.

[0190] Next, a reaction gas is supplied. The reaction gas may be any reaction gas commonly used in the art, and preferably contains a nitriding agent. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0191] Preferably, the nitriding agent may be nitrogen (N2), hydrazine gas (N2H4) or a mixture of nitrogen and hydrogen.

[0192] Next, the unreacted residual reaction gas is purged with an inert gas, thereby removing not only the excess reaction gas but also the generated by-products.

[0193] As described above, as an example, the above-mentioned thin film forming method can take the following steps as a unit cycle, repeat the above-mentioned unit cycle to form a thin film of desired thickness, and the above-mentioned steps include: a step of supplying a masking substance onto a substrate; a step of purging the masking substance that is not adsorbed; a step of adsorbing a precursor compound / thin film forming composition onto a substrate; a step of purging the precursor compound that is not adsorbed; a step of adsorbing a diffusion improving substance onto a substrate; a step of purging the diffusion improving substance that is not adsorbed; a step of supplying a reaction gas; and a step of purging the residual reaction gas.

[0194] As an example, the number of repetitions of the unit cycle may be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired film properties can be well expressed.

[0195] The present invention also provides a semiconductor substrate manufactured by the thin film forming method of the present invention, in which the step coverage and thickness uniformity of the thin film are excellent, and the density and electrical characteristics of the thin film are excellent.

[0196] Preferably, the thickness of the above-mentioned thin film is less than 20nm, based on the film thickness of 10nm, the resistivity value is less than 400μΩ·cm or 50~400μΩ·cm, the halogen content is less than 10,000ppm, and the step coverage is more than 90%. Within this range, it performs excellently as an anti-diffusion film and has the effect of reducing corrosion of metal wiring materials, but is not limited to this.

[0197] As an example, the thickness of the thin film may be 0.1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 20 nm, and even more preferably 5 to 20 nm. Within this range, the film has excellent properties.

[0198] As an example, based on a film thickness of 10 nm, the resistivity value of the above-mentioned film can be 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. Within this range, the film has excellent film properties.

[0199] The halogen content of the film may be 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 film has excellent properties and a reduced film growth rate. As an example, the halogen remaining in the film may be Cl2, Cl or Cl -The lower the residual halogen content in the film, the better the film quality is, so it is preferred.

[0200] As an example, the step coverage of the above-mentioned film can be above 90%, preferably above 92%, and more preferably above 95%. Within this range, even a thin film with a complex structure can be easily deposited on the substrate. Therefore, it has the advantage of being applicable to a new generation of semiconductor devices.

[0201] Preferably, the thickness of the above-mentioned film is less than 20nm, and the content of carbon, nitrogen and halogen is less than 10,000ppm based on the film thickness of 10nm, and the step coverage is more than 90%. Within this range, it has excellent performance as a dielectric film or barrier film, but is not limited to this.

[0202] As an example, the film may be a two-layer or three-layer multilayer structure, preferably a two-layer or three-layer multilayer structure, as required. As a specific example, the two-layer multilayer film may be a structure of a lower film-middle film, and as a specific example, the three-layer multilayer film may be a structure of a lower film-middle film-upper film.

[0203] As an example, the above-mentioned lower layer film may include one or more selected from Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0204] As an example, the intermediate layer film may include Ti x N y , preferably, may contain TN.

[0205] As an example, the upper layer film may include one or more selected from W and Mo.

[0206] Below, preferred embodiments and drawings are proposed to help understand the present invention. Those skilled in the art understand that the following embodiments and drawings are only used to illustrate the present invention, and various changes and modifications can be made within the scope of the scope of the present invention and technical ideas, and these deformations and modifications belong to the scope of the attached invention application patent.

[0207] [Example]

[0208] Examples 1 to 3, Comparative Examples 1 to 2

[0209] Using the components shown in Table 1, Figure 1 An ALD deposition process is performed.

[0210] Figure 1This is a diagram schematically showing the deposition process sequence of the present invention mainly in one cycle.

[0211] Specifically, a compound represented by the following chemical formula 2-1 is prepared as a 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 are prepared as diffusion improving substances.

[0212] [Chemical formula 2-1]

[0213]

[0214] [Chemical formula 4-1]

[0215]

[0216] [Chemical formula 4-2]

[0217]

[0218] [Chemical formula 4-3]

[0219]

[0220] 90 parts by weight of the compound represented by the above Chemical Formula 2-1 and 10 parts by weight of the compound represented by the above Chemical Formula 4-1 were mixed as a film modifying composition and designated as Composition 1 in Table 1.

[0221] 90 parts by weight of the compound represented by the above Chemical Formula 2-1 and 10 parts by weight of the compound represented by the above Chemical Formula 4-2 were mixed as a film modifying composition and designated as Composition 2 in Table 1.

[0222] 80 parts by weight of the compound represented by the above Chemical Formula 2-1 and 20 parts by weight of the compound represented by the above Chemical Formula 4-3 were mixed as a film modifying composition and designated as Composition 3 in Table 1.

[0223] In addition, trimethylaluminum (indicated as TMA in the table) was prepared as a precursor.

[0224] like Figure 1As shown, the prepared film modification composition or shielding material or diffusion improving material is placed in a tank and supplied to a vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. After the shielding material vaporized into a vapor phase in the vaporizer is put into a deposition chamber loaded with a substrate for 1 second, argon gas is supplied at 5000 sccm for 2 seconds to perform argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr.

[0225] Next, after the precursor is loaded into a can and introduced into the deposition chamber through a vapor flow controller (VFC) in the manner shown in Table 1, argon gas is supplied at 5000 sccm for 2 seconds to perform argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr.

[0226] Next, ozone as a reactive gas was introduced into the reaction chamber at 1000 sccm for 3 seconds, and then argon gas was purged 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.

[0227] This process was repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0228] The deposition rate reduction rate (DR reduction rate) and SIMS C impurities and step coverage of each of the obtained thin films of Examples 1 to 3 and Comparative Examples 1 and 2 were measured in the following manner.

[0229] *Deposition rate reduction rate (DR (dep.rate) reduction rate): It indicates the ratio of the deposition rate reduction after the addition of the film modification composition compared to the DR before the addition of the film modification composition. Calculate the percentage value.

[0230] Specifically, the thickness of the film measured by an ellipsometer is divided by the number of cycles to calculate the thickness of the film deposited per cycle, thereby calculating the reduction rate of the film growth rate, wherein the ellipsometer is a device that can measure optical properties such as the thickness or refractive index of the manufactured film using the polarization properties of light. Specifically, the calculation is performed using Mathematical Formula 1.

[0231] [Mathematical formula 1]

[0232] Deposition rate (DR) reduction rate = [{(DR i )-(DR f )} / (DR i)]×100

[0233] (In this formula, DR (Deposition rate), ) is the rate of film deposition. When depositing a film formed from a precursor and a reactant, DR i Initial deposition rate is the deposition rate of a thin film without adding diffusion-improving substances. f The final deposition rate is the deposition rate of the thin film formed by adding the diffusion-improving material during the above process. The deposition rate (DR) is the value of the film with a thickness of 3 to 30 nm measured by an ellipsometer under normal temperature and pressure conditions. The unit used is )

[0234] *Non-uniformity: The maximum and minimum thicknesses of the thin films measured by the above-mentioned ellipsometer were selected, and the results calculated by mathematical formula 2 are shown in Tables 1 and Figure 2 Specifically, the thickness of the four edge parts and one center part of the 300 mm wafer were measured.

[0235] [Mathematical formula 2]

[0236] Unevenness % = [{(maximum thickness - minimum thickness) / 2}×average thickness]×100

[0237] *SIMS (Secondary-ion mass spectrometry) C impurities: Ion sputtering was used to dig into the film axially, and the C impurity counts were considered when the sputtering time was 50 seconds where there was less contamination on the surface layer of the substrate, and the C impurity value was confirmed in the SIMS graph.

[0238] *Step coverage (%): The TEM of the sample was measured and calculated using Formula 3, wherein the sample was horizontally cut 100 nm downward from the top (left figure) and 100 nm upward from the bottom (right figure) for the thin film deposited on a complex structure substrate with an aspect ratio of 22:1 by Examples 1 to 3 and Comparative Examples 1 to 2.

[0239] [Mathematical formula 3]

[0240] Step coverage % = (thickness deposited on the lower inner wall / thickness deposited on the upper inner wall) × 100

[0241] Specifically, for a substrate with a complex structure having an aspect ratio of 22:1, with an upper diameter of 90nm, a lower diameter of 65nm, and a via hole depth of about 2000nm, after a deposition process was performed using diffusion-improving material application conditions, in order to confirm the thickness uniformity and step coverage of the inside of the vertically formed via hole, a sample was prepared by horizontally cutting 100nm downward from the upper part and 100nm upward from the lower part, and the measurement was performed using a transmission electron microscope (TEM) and is shown in Table 1. Figures 3 to 5 middle.

[0242] Table 1

[0243]

[0244]

[0245] As shown in Table 1, it was confirmed that Examples 1 to 3 using the thin film modification composition of the present invention had significantly improved deposition rate reduction and uniformity compared to Comparative Example 1 not using the thin film modification composition of the present invention.

[0246] In addition, it was confirmed that Examples 1 to 3 using the thin film modification composition of the present invention had the same or similar deposition rate reduction ratio as Comparative Example 2 using a type other than the appropriate type, and had excellent uniformity.

[0247] In particular, it was confirmed that Examples 1 to 3 using the film modification composition of the present invention had a uniformity higher by 20% or more than that of Comparative Example 1 not using the film modification composition or Comparative Example 2 using the masking material alone (see Figure 2 ).

[0248] Furthermore, if Figures 3 to 5 As shown, it was confirmed that the step coverage of Examples 1 to 3 using the film modifying composition of the present invention was 99.1% to 100.2%, which was significantly improved compared to 95.0% of Comparative Example 1 not using the film modifying composition.

Claims

1. A film modification composition, characterized in that: Include: 50 to 99 parts by weight of a shielding substance, wherein the shielding substance contains one or more lone electron pairs selected from oxygen, sulfur and phosphorus; and 1 to 50 parts by weight of a diffusion improving substance; The boiling point of the diffusion improving substance is in the range of 5 to 200°C.

2. The film modification composition according to claim 1, characterized in that The shielding substance is a compound represented by Chemical Formula 1 to Chemical Formula 2. [Chemical formula 1] [Chemical formula 2] In the above chemical formulas 1 to 2, R' and R" are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, A is oxygen, sulfur, phosphorus, nitrogen, -CH or -CH2, The above-mentioned B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3 or -SCH2CH3, m is an integer from 0 to 3.

3. The film modification composition according to claim 1, characterized in that The shielding material includes 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. [Chemical formula 1-1 to Chemical formula 1-4] [Chemical formula 2-1 to Chemical formula 2-4] 4. The film modification composition according to claim 1, characterized in that The diffusion improving substance is at least one selected from octane, ether, dichloromethane, toluene, hexane and ethanol.

5. The film modification composition according to claim 1, characterized in that The above film modification composition is used to control the reaction surface of the film. The above-mentioned thin film is formed by one or more precursor compounds 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.

6. A method for forming a thin film, characterized in that: The following steps are involved: Injecting a thin film modifying composition into the chamber to mask the surface of the loaded substrate, The above-mentioned film modification composition comprises: 50 to 99 parts by weight of a shielding substance, wherein the shielding substance contains one or more lone electron pairs selected from oxygen, sulfur and phosphorus; and 1 to 50 parts by weight of a diffusion improving substance, The boiling point of the diffusion improving substance is in the range of 5 to 200°C.

7. The thin film forming method according to claim 6, characterized in that: The above chamber is an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

8. The thin film forming method according to claim 6, characterized in that: The film modification composition is transported into the chamber by VFC method, DLI method or LDS method. The above-mentioned 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, characterized in that: Comprising a thin film manufactured according to the thin film forming method according to claim 6.

10. The semiconductor substrate according to claim 9, characterized in that The film is a multi-layer structure of two or more layers.

11. A semiconductor device, characterized in that: Comprising the semiconductor substrate according to claim 10.

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