Oxide film reaction surface control agent and oxide film formation method using the same

Abstract

The present invention relates to an oxide film reaction surface control agent, an oxide film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. A compound having a predetermined structure is provided as an oxide film reaction surface control agent, and a deposition (sediment) layer of uniform thickness is formed on a substrate as a shielding region due to the difference in the adsorption distribution pattern of the oxide film reaction surface control agent, thereby reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate, 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 can be significantly improved and impurities can be reduced.

Description

[Technical field]

[0001] The present invention relates to an oxide film reaction surface control agent, a method for forming an oxide film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. More particularly, the present invention relates to an oxide film reaction surface control agent that provides a compound of a predetermined structure as an oxide film reaction surface control agent, and forms a deposition layer of uniform thickness on a substrate as a shielding region due to differences in adsorption distribution patterns, thereby reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate, thereby significantly improving step coverage and uniformity of the thin film thickness even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurities, and a method for forming an oxide film using the same, and a semiconductor substrate manufactured therefrom. [Background technology]

[0002] Due to increasing integration of memory and non-memory semiconductor devices, substrate topologies are becoming increasingly complex.

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

[0004] As a result, step coverage, which defines 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%, making it increasingly difficult for devices to exhibit electrical characteristics, and its importance is increasing. 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 bring step coverage as close to 100% as possible.

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

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

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

[0008] When the deposition temperature is increased in order to realize 100% step coverage, step coverage is difficult. First, in a deposition process consisting of two processes, a precursor and a reactant, an increase in deposition temperature causes a rapid increase in the thin film growth rate (GPC). In addition, even if an 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 it is not considered a solution.

[0009] In addition, high-temperature processes are required to realize high-quality metal oxide films for semiconductor devices. Research results have been reported that increasing the deposition temperature of atomic layers to 400°C reduces the concentration of carbon and hydrogen remaining in the thin film (see paper in J. Vac. Sci. Technol. A, 35(2017) 01B130).

[0010] However, the higher the deposition temperature, the more difficult it is to ensure the step coverage. First, in a deposition process consisting of two steps, a precursor and a reactant, an increase in deposition temperature can cause a rapid increase in GPC (thin film growth rate). Even if a known shielding agent is used to mitigate the increase in GPC (thin film growth rate) caused by an increase in deposition temperature, it has been confirmed that the GPC (thin film growth rate) increases by about 10% at 300°C. In other words, when deposition is performed at 360°C or higher, it becomes difficult to expect the effect of reducing GPC (thin film growth rate) provided by conventionally known shielding agents.

[0011] Therefore, there is a need to develop a method for forming a thin film that can effectively form a thin film with a complex structure even at high temperatures, has a low amount of residual impurities, and greatly improves step coverage and thickness uniformity of the thin film, and semiconductor substrates manufactured therefrom. Summary of the Invention [Problem to be solved by the invention]

[0012] In order to solve the above-mentioned problems of the prior art, the present invention aims to provide an oxide film reaction surface control agent that forms a deposition layer of uniform thickness on a substrate as a shielding region for a thin film by difference in adsorption distribution pattern of the oxide film reaction surface control agent, reduces the deposition rate of the thin film, and appropriately lowers 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, a method for forming an oxide film using the same, and a semiconductor substrate manufactured using the same.

[0013] The present invention aims to improve the crystallinity and oxidation fraction of a thin film, thereby improving the density and dielectric properties of the thin film.

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

[0015] In order to achieve the above-mentioned object, the present invention provides an oxide film reaction surface control agent, which contains one or more compounds selected from a cyclic compound having three or more element species having an unshared electron pair and a linear (straight-chain) compound having three or more element species having an unshared electron pair, and is characterized in that it controls the reaction surface of an oxide film material made of one or more metals selected from a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal.

[0016] The unshared electron pair may be one or more selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

[0017] The cyclic compound having three or more element species having an unshared electron pair may be a compound represented by the following Chemical Formula 1.

[0018] [Chemical formula 1] TIFF0007645374000001.tif56128

[0019] (In the above Chemical Formula 1, the R' is 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, A is oxygen (O), sulfur (S), phosphorus (P), or nitrogen (N); The m is an integer of 0 to 2.

[0020] The linear compound having three or more elemental species having an unshared electron pair may be a compound represented by the following Chemical Formula 2.

[0021] [Chemical formula 2] TIFF0007645374000002.tif34128

[0022] (In the above Chemical Formula 2, the above R″ is hydrogen, 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 B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3.

[0023] The oxide film reaction surface control agent may have a refractive index (measured at 20 to 25° C.) of 1.365 to 1.48, 1.366 to 1.47, 1.367 to 1.46, 1.365 to 1.41, or 1.41 to 1.46.

[0024] The oxide film reaction surface control agent may include one or more compounds selected from the compounds represented by the following Chemical Formulae 1-1 to 1-3 and 2-1 to 2-3.

[0025] [Chemical formula 1-1~1-3] TIFF0007645374000003.tif22118

[0026] [Chemical formula 2-1~2-3] TIFF0007645374000004.tif20118

[0027] The metal can control the reaction surface of an oxide film 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.

[0028] The present invention also relates to Treating the surface of the substrate with the oxide film reaction surface inhibitor; and a step of sequentially injecting a precursor compound and a reaction gas into a chamber to form an oxide film on the surface of the loaded substrate.

[0029] The chamber can be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0030] The substrate surface treatment step may be performed by applying the oxide film reaction surface control agent to the substrate loaded in a chamber at 20 to 800°C.

[0031] The oxide film reaction surface control agent and the precursor compound are transferred into the chamber by a VFC method, a DLI method, or an LDS method, and the thin film may be a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a tellurium oxide film.

[0032] The reactive gas may include O2, O3, N2O, NO2, H2O, or a plasma of O2.

[0033] The oxide film may be a thin film having one or more layers of one or more metals selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd.

[0034] 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.

[0035] The oxide film forming method includes: i) vaporizing the oxide film reaction surface control agent to form a shielding region on a surface of a substrate loaded in a chamber; ii) initially purging the interior of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it in an area outside said shielded area; iv) second purging the interior of the chamber with a purge gas; v) supplying a reactive gas into the chamber; and vi) tertiary purging of the inside of the chamber with a purge gas.

[0036] The substrate having an activated reactive surface in the reactive surface activation step may be prepared by applying the oxide film reactive surface control agent to the substrate loaded in a chamber at 20 to 800°C.

[0037] The precursor compound may be a molecule composed of one or more selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may be a precursor having a vapor pressure at 25° C. of more than 0.01 mTorr and not more than 100 Torr.

[0038] The precursor compound, or the precursor compound after it has been vaporized and injected, may include a plasma post-treatment step.

[0039] In the steps ii) and iv), the amount of the purge gas introduced into the chamber may be 10 to 100,000 times the volume of the oxide film reaction surface control agent introduced.

[0040] The reaction gas is an oxidant, and the reaction gas, the oxide film reaction surface control agent and the precursor compound can be delivered into the chamber by a VFC method, a DLI method or an LDS method.

[0041] The substrate loaded into the chamber is heated to 100 to 800° C., and the ratio of the oxide film reaction surface control agent and the precursor compound input into the chamber (mg / cycle) may be 1:1 to 1:20.

[0042] The present invention also provides a semiconductor substrate comprising an oxide film produced by the above-mentioned method for forming an oxide film.

[0043] The oxide film may have a multi-layer structure of two layers or three or more layers.

[0044] The present invention also provides a semiconductor device including the semiconductor substrate described above.

[0045] 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

[0046] According to the present invention, there is an effect of providing an oxide film reaction surface control agent that effectively blocks adsorption to the substrate surface, reduces the reaction rate, and appropriately lowers the thin film growth rate, thereby improving step coverage even when a thin film is formed on a substrate having a complex structure.

[0047] In addition, during the formation of the thin film, process by-products 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.

[0048] In addition, the process by-products during the thin film formation can be reduced, and the step coverage and thin film density can be improved, and further, an oxide film forming method using the same and a semiconductor substrate manufactured therefrom can be provided. [Brief description of the drawings]

[0049] [Figure 1] 1 is a diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle. [Diagram 2]TEM photographs showing the thicknesses of the upper (100 nm below the top) and lower (100 nm above the bottom) cross sections of an oxide film deposited without using an oxide film reaction surface control agent according to Comparative Example 1, and the thicknesses of the upper (100 nm below the top) and lower (100 nm above the bottom) cross sections of an oxide film deposited using an oxide film reaction surface control agent. [Diagram 3] TEM photographs showing the thicknesses of the upper (100 nm below the top) and lower (100 nm above the bottom) cross sections of an oxide film deposited using an oxide film reaction surface control agent according to Example 3, and the thicknesses of the upper (100 nm below the top) and lower (100 nm above the bottom) cross sections of an oxide film deposited using an oxide film reaction surface control agent according to Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0050] The oxide film reaction surface control agent of the present invention, the method for forming an oxide film using the same, and the semiconductor substrate manufactured therefrom will be described in detail below.

[0051] In this description, unless otherwise specified, "reactive surface control" means that the surface of the substrate used as the reactive surface in the deposition process is controlled so that the precursor compound is adsorbed onto the substrate surface with a reduced reaction rate.

[0052] In this description, unless otherwise specified, the term "shielding" means not only reducing, preventing or blocking precursor compounds for forming a thin film from being adsorbed onto a substrate, but also reducing, preventing or blocking process by-products from being adsorbed onto a substrate.

[0053] The present inventors have confirmed the following. That is, the precursor compound for forming an oxide film on a substrate loaded inside a chamber uses a compound with a specific structure as an oxide film reaction surface control agent that reduces the adsorption speed of the reacting reaction surface, and due to the difference in the adsorption distribution map of the oxide film reaction surface control agent, a deposition layer of uniform thickness is formed in a shielding region where it does not remain in the thin film, so a relatively thin thin film is formed and the growth rate of the formed thin film is significantly reduced. Therefore, even when applied to a substrate with a complex structure at high temperatures, the uniformity of the thin film is ensured, and the step coverage is greatly improved, and deposition at a particularly thin thickness is possible. It has also been confirmed that the amount of O, Si, metal, metal oxide, and even the amount of carbon remaining as process by-products, which was difficult to reduce, is improved. Based on this, the inventors have been researching oxide film reaction surface control agents that provide a shielding region, and have completed the present invention.

[0054] The oxide film reaction surface control agent of the present invention controls the reaction surface on the substrate where an oxide film is formed.

[0055] The thin film can be provided, for example, by using one or more precursors selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and can provide an oxide film, a nitride film, a metal film, or a selective thin film shielding region for these, and in this case, the effect to be achieved by the present invention can be fully obtained.

[0056] Specific examples of the thin film include a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, and a tellurium oxide film.

[0057] 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.

[0058] In the present invention, the precursor compound used to form a thin film may be a molecule having one or more central metal atoms (M) selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and one or more ligands consisting of C, N, O, H, X (halogen), and Cp (cyclopentadiene), and may be a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C.

[0059] As an example of the precursor compound, a compound represented by the following Chemical Formula 3 can be used.

[0060] [Chemical formula 3] TIFF0007645374000005.tif47128

[0061] (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; L1, L2, L3, and L4 are -H, -X, -R, -OR, -NR2, or Cp (cyclopentadiene), which may be the same or different from each other; where -X is F, Cl, Br, or I; -R is a C1-C10 alkyl, a C1-C10 alkene, or a C1-C10 alkane, which may be linear or cyclic; and L1, L2, L3, and L4 may be formed from 2 to 6 depending on the oxidation value of the central metal.)

[0062] For example, when the central metal is divalent, L1 and L2 may be attached to the central metal as ligands, and when the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 may be attached to the central metal, and the ligands corresponding to L1 to L6 may be the same or different from each other.

[0063] The M may be a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal, and is preferably hafnium (Hf), zirconium (Zr), aluminum (Al), niobium (Nb), or tellurium (Te, Tellurium). In this case, there are advantages such as a large reduction effect of process by-products, excellent step coverage, an effect of improving the thin film density, and excellent electrical properties, insulating properties, and dielectric properties of the thin film.

[0064] The L1, L2, L3, and L4 are -R, -X, or Cp, which may be the same or different from each other, where -R is a C1-C10 alkyl, a C1-C10 alkene, or a C1-C10 alkane, and may have a linear or cyclic structure.

[0065] In addition, L1, L2, L3 and L4 may be the same or different from each other as -NR2 or Cp, where -R can be C1-C10 alkyl, C1-C10 alkene, or C1-C10 alkane, iPr, or tBu.

[0066] In addition, in the above formula 8, L1, L2, L3, and L4 are -H or -X, which may be the same or different, and where -X may be F, Cl, Br, or I.

[0067] Specifically, examples of aluminum precursor compounds that can be used include Al(CH3)3 and AlCl4.

[0068] 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.

[0069] The oxide film reaction surface control agent of the present invention can reduce the rate at which the precursor compound is adsorbed onto the substrate by previously controlling the reaction surface that adsorbs the precursor compound onto the substrate.

[0070] For example, the shielding region may be formed on the entire substrate or a portion of the substrate on which the thin film is formed.

[0071] Furthermore, if the total area of ​​the entire substrate or part of the substrate is taken as 100%, the shielded region may, for example, occupy 10 to 95% of the substrate area, specifically 15 to 90% of the substrate area, preferably 20 to 85% of the substrate area, more preferably 30 to 80% of the substrate area, more preferably 40 to 75% of the substrate area, and even more preferably 40 to 70% of the substrate area, and the unshielded region may occupy the remaining substrate area.

[0072] Furthermore, if the total area of ​​the entire substrate or part of the substrate is taken as 100%, the first shielded region may occupy 10 to 95% of the substrate area, specifically 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70% of the substrate area, and the second shielded region may occupy 10 to 95% of the remaining substrate area, specifically 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70%, and the remaining substrate area may be an unshielded region.

[0073] The oxide film reaction surface control agent can provide a controlled reaction surface on the surface of the substrate on which the thin film is provided.

[0074] The oxide film reaction surface control agent may include a linear or cyclic saturated hydrocarbon or a linear saturated hydrocarbon having 3 to 15 carbon atoms and having 3 or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S). In this case, a shielding region that does not remain in the thin film during thin film formation is formed, forming a relatively thin thin film, suppressing side reactions and controlling the thin film growth rate, reducing process by-products in the thin film, thereby reducing corrosion and deterioration, improving the crystallinity of the thin film, and reaching a stoichiometric oxidation state during the formation of a metal oxide film. Even when a thin film is formed on a substrate having a complex structure, there is an effect of greatly improving step coverage and thickness uniformity of the thin film.

[0075] As a specific example, the oxide film reaction surface control agent has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) independently at both ends of a central carbon atom connected to oxygen by a double bond, and thus may have a large effect of reducing process by-products, excellent step coverage, an effect of improving the thin film density, and excellent electrical properties of the thin film.

[0076] Here, the structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) independently at both ends of the central carbon atom connected to the oxygen by a double bond as described above, unless otherwise specified, TIFF0007645374000006.tif29128 Refers to.

[0077] As a specific example, the oxide film reaction surface control agent has a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to oxygen by a double bond and carbon (C) at the other end, which can result in a large reduction in process by-products, excellent step coverage, improved thin film density, and superior electrical properties of the thin film.

[0078] Here, a structure containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) at one end of a central carbon atom connected to the above-mentioned oxygen via a double bond and carbon (C) at the other end is, unless otherwise specified, TIFF0007645374000007.tif29128 Refers to.

[0079] The oxide film reaction surface control agent is characterized by including one or more compounds selected from a cyclic compound having three or more element species having an unshared electron pair and a linear compound having three or more element species having an unshared electron pair, and in this case, the reaction surface of an oxide film material made of one or more metals selected from trivalent metals, tetravalent metals, pentavalent metals, and hexavalent metals is controlled, and a relatively thin thin film is formed, while side reactions are suppressed and the thin film growth rate is controlled, thereby reducing process by-products in the thin film and reducing corrosion and deterioration, and the crystallinity of the thin film is improved, and a stoichiometric oxidation state is reached when a metal oxide film is formed, and even when a thin film is formed on a substrate having a complex structure, there is an effect of greatly improving step coverage and uniformity of the thin film thickness.

[0080] The unshared electron pair may be one or more selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

[0081] The oxide film reaction surface control agent may be at least one selected from the group consisting of compounds represented by the following formulas 1 and 2. In this case, when forming a thin film, a shielding region that does not remain in the thin film is formed, forming a relatively sparse (thin) thin film, and controlling the thin film growth rate by suppressing side reactions, thereby reducing process by-products in the thin film, reducing corrosion and deterioration, and improving the crystallinity of the thin film. Even when forming a thin film on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0082] [Chemical formula 1] TIFF0007645374000008.tif56128

[0083] (In the above Chemical Formula 1, the R' is hydrogen, 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), or nitrogen (N), and the m is an integer of 0 to 2.)

[0084] The linear compound having three or more elemental species having an unshared electron pair may be a compound represented by the following chemical formula 2.

[0085] [Chemical formula 2] TIFF0007645374000009.tif34128

[0086] (In the above Chemical Formula 2, R″ is hydrogen, 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 B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3.

[0087] These oxide film reaction surface control agents may be provided alone or in the form of a mixed gas, and may have a large effect of reducing process by-products, excellent step coverage, an effect of improving the thin film density, and excellent electrical properties of the thin film.

[0088] In the above Chemical Formula 1, R' is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkene group having 1 to 5 carbon atoms, and is preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkene group having 1 to 3 carbon atoms. In this case, there are advantages such as a large effect of reducing process by-products, excellent step coverage, an effect of improving thin film density, and excellent electrical properties, insulating properties, and dielectric properties of the thin film.

[0089] 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 more excellent.

[0090] The above m is an integer of 0 to 2, and preferably an integer of 1 to 2.

[0091] In the above Chemical Formula 2, R″ is an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. In this case, there are advantages such as a large effect of reducing process by-products, excellent step coverage, an effect of improving the thin film density, and better electrical properties of the thin film.

[0092] In the above Chemical Formula 2, B is -OCH3, -OCH2CH3, -OCHCH3, -SH, -SCH3, or -SCH2CH3, and preferably -OCH3, -OCH2CH3, or -OCHCH3. 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 more excellent.

[0093] As a specific example, the oxide film reaction surface control agent may include at least one compound selected from the compounds represented by the following formulas 1-1 to 1-3 and 2-1 to 2-3. In this case, it has a great effect of controlling the growth rate of the thin film by providing a thin film shielding region, a great effect of removing process by-products, and an excellent effect of improving step coverage and film quality.

[0094] [Chemical formula 1-1~1-3] TIFF0007645374000010.tif22118

[0095] [Chemical formula 2-1~2-3] TIFF0007645374000011.tif20118

[0096] When the oxide film reaction surface control agent is used, due to the difference in the adsorption distribution diagram for the activator having the above-mentioned structure, a deposition layer of uniform thickness is formed in the shielding region where no thin film remains, forming a relatively thin thin film and significantly reducing the growth rate of the formed thin film. Therefore, even when applied to a substrate having a complex structure, the uniformity of the thin film is ensured, the step coverage is greatly improved, and deposition at a particularly thin thickness is possible. In addition, it is possible to provide an effect of improving O, Si, metal, metal oxide, which remain as process by-products, and even the carbon residue, which was previously difficult to reduce.

[0097] The oxide film reaction surface control agent may have a refractive index of 1.365 to 1.48, 1.366 to 1.393, or 1.367 to 1.391. In this case, by controlling in advance the reaction surface to provide an oxide film on the substrate surface, the reaction rate can be improved, step coverage and thickness uniformity of the thin film can be significantly improved even when a thin film is formed on a substrate having a complex structure, and the agent has the advantages of effectively protecting the substrate surface by preventing the adsorption of not only the thin film precursor but also the process by-products, and effectively removing the process by-products.

[0098] The reactive gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0099] The oxide film may be a thin film having one or more layers of one or more metals selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd.

[0100] The oxide film reaction surface control agent can provide a shielding region for the thin film.

[0101] The thin film shielding region is characterized in that it does not remain on the thin film.

[0102] 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 elements at less than 0.1 atomic % (atom %) when analyzed by XPS. More preferably, in a Secondary-ion Mass Spectrometry (SIMS) measurement method or X-ray Photoelectron Spectroscopy (XPS) measurement method in which the substrate is measured while being dug in the depth direction, when the sensitization rates of C, N, Si, and halogen impurities are considered before and after using an oxide film reaction surface control agent under the same deposition conditions, it is preferable that the sensitization rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0103] For example, the oxide film may contain halogen compounds at 100 ppm or less.

[0104] The oxide 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, but is not limited thereto.

[0105] The oxide film reaction surface control agent and the precursor compound may preferably be a compound having a purity of 99.9% or more, a compound having a purity of 99.95% or more, or a compound having a purity of 99.99% or more. For reference, when a compound having a purity of less than 99% is used, impurities may remain in the thin film or cause a side reaction with the precursor or reactant, so it is preferable to use a substance having a purity of 99% or more.

[0106] The oxide film reaction surface control agent is preferably used in an atomic layer deposition (ALD) process, and in this case, has the advantages of effectively protecting the surface of a substrate as an oxide film reaction surface control agent and effectively removing process by-products without interfering with the adsorption of a precursor compound.

[0107] The oxide film reaction surface control agent is preferably liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20° C.) is 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, a shielding region is effectively formed, and there is an effect of excellent step coverage, thin film thickness uniformity, and improved film quality.

[0108] More preferably, the oxide film reaction surface control agent 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, a shielding region can be effectively formed, and there is an effect of excellent step coverage, thin film thickness uniformity, and improved film quality.

[0109] The method for forming an oxide film of the present invention includes the steps of treating a surface of a substrate with the above-mentioned oxide film reaction surface control agent; and sequentially injecting a precursor compound and a reaction gas into a chamber to load the treated substrate, thereby forming an oxide film on the surface of the loaded substrate. In this case, a thin film shielding region is formed on the substrate to reduce the deposition rate of the thin film and appropriately reduce the thin film growth rate, thereby significantly improving step coverage and thickness uniformity of the thin film even when a thin film is formed on a substrate having a complex structure.

[0110] In the step of treating the surface of the substrate with the oxide film reaction control agent, the time (Feeding Time, sec) for supplying the oxide film reaction control agent 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.

[0111] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle with a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle with a chamber volume of 18 L.

[0112] As a preferred embodiment, the oxide film forming method may include the steps of: i) vaporizing the oxide film reaction surface control agent and treating the surface of a substrate loaded into a chamber; ii) primarily purging the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it onto the surface of a substrate loaded into the chamber; iv) secondly purging the interior of the chamber with a purge gas; v) supplying a reaction gas into the chamber; and vi) thirdly purging the interior of the chamber with a purge gas.

[0113] Here, 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. In this manner, when the oxide film reaction surface control agent of the present invention is added prior to the precursor compound within one cycle to be adsorbed on the substrate, there are advantages in that the thin film growth rate can be appropriately reduced even when deposition is performed at a high temperature, the generated process by-products can be effectively removed, the resistivity of the thin film can be reduced, and the step coverage can be greatly improved.

[0114] As yet another preferred embodiment, the substrate having a controlled reaction surface in the reaction surface controlling step may be manufactured by applying the oxide film reaction surface control agent to the substrate loaded in a chamber at 20 to 800°C.

[0115] As a preferred example, the oxide film forming method of the present invention can activate the surface of a substrate by adding the oxide film reaction surface control agent of the present invention before a precursor compound in one cycle, and then add the precursor compound to adsorb to the substrate. In this case, even if a 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 and step coverage can be significantly improved. The crystallinity of the thin film can be increased, so that the resistivity of the thin film can be reduced. Even when applied to a semiconductor device having a large aspect ratio, the thickness uniformity of the thin film can be significantly improved, ensuring the reliability of the semiconductor device.

[0116] In the oxide film forming method, for example, when the precursor compound 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 these ranges, a desired thin film thickness can be obtained, and the effects to be achieved by the present invention can be sufficiently obtained.

[0117] The precursor compound is a molecule having one or more central metal atoms (M) selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and one or more ligands consisting of C, N, O, H, X (halogen), and Cp (cyclopentadiene), and has a vapor pressure of 1 mTorr to 100 Torr at 25° C., and can maximize the effect of forming a shielding region by the oxide film reaction surface control agent described above, even though it is natural oxidation.

[0118] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0119] The thin film may be a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a tellurium oxide film.

[0120] In the present invention, the precursor compound or precursor compounds may include a step of performing plasma post-treatment after being vaporized and injected, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0121] In the case where the oxide film reaction surface control agent is first adsorbed on the substrate, the precursor compound is then adsorbed on the substrate, and the precursor compound is then adsorbed on the substrate, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed oxide film reaction surface control agent is not particularly limited as long as it is an amount sufficient to remove the unadsorbed oxide film reaction surface control agent, and 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 oxide film reaction surface control agent is sufficiently removed, so that a thin film is formed uniformly and deterioration of the film quality can be prevented. Here, the amounts of the purge gas and the oxide film reaction surface control agent introduced are based on one cycle, and the volume of the oxide film reaction surface control agent means the volume of the vaporized oxide film reaction surface control agent.

[0122] As a specific example, when the injection amount of the oxide film reaction surface control agent is 200 sccm and the purge gas in the step of purging the unadsorbed oxide film reaction surface control agent is at a flow rate of 5000 sccm, the injection amount of the purge gas is 25 times the injection amount of the oxide film reaction surface control agent.

[0123] In addition, 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, more preferably 100 to 10,000 times, based on the volume of the precursor compound introduced into the chamber, and within this range, the unadsorbed precursor compound is sufficiently removed, so that a thin film is formed uniformly and deterioration of the film quality can be prevented. 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.

[0124] In addition, the amount of purge gas introduced into the chamber in the purging step performed immediately after the reaction gas supply step may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times the volume of the reaction gas introduced into the chamber, and within this range, the desired effect can be sufficiently obtained. Here, the amounts of purge gas and reaction gas introduced are each based on one cycle.

[0125] The precursor compound and the precursor compound can be preferably delivered into the chamber by a VFC method, a DLI method or an LDS method, and more preferably are delivered into the chamber by an LDS method.

[0126] The substrate loaded in the chamber may be heated to, for example, 100 to 650°C, specifically, 150 to 550°C, and the oxide film reaction surface control agent or precursor compound may be injected onto the substrate in a heated or unheated state. Depending on the deposition (deposition) efficiency, the agent or precursor compound may be injected unheated and then the heating conditions may be adjusted during the deposition (deposition) process. For example, the agent or precursor compound may be injected onto the substrate at 100 to 650°C for 1 to 20 seconds.

[0127] The ratio of the precursor compound and the oxide film reaction surface control agent input into the chamber (mg / cycle) may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and the effect of reducing process by-products are large.

[0128] In the oxide film forming method, when the oxide film reaction surface control agent and the precursor compound are used, the reduction rate of the deposition rate shown in the following formula 1 can be 45% or more, specifically 48% or more, preferably 52% or more. In this case, the oxide film reaction surface control agent having the above-mentioned structure is used to form a deposition layer of uniform thickness into a thin film, and a relatively thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the film is applied to a substrate with a complex structure under high temperature, the uniformity of the thin film is ensured and the step coverage is greatly improved. In particular, deposition at a thin thickness is possible, and the effect of improving O, Si, metal, metal oxide, which remain as process by-products, and even the carbon residue, which was difficult to reduce in the past, can be provided.

[0129] [Formula 1] Deposition rate reduction rate = [{(DRi)-(DRf)} / (DRi)] x 100

[0130] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. In the deposition of a thin film formed from a precursor and a reactant, DRi (initial deposition rate) is the deposition rate of a thin film formed without adding a reaction surface control agent. DRf (final deposition rate) is the deposition rate of a thin film formed by adding an oxide film reaction surface control agent during the above process. Here, the deposition rate (DR) is a value measured at room temperature and pressure using an ellipsometer device for a thin film with a thickness of 3 to 30 nm, and is expressed in units of Å / cycle.)

[0131] In Equation 1, the thin film growth rate per cycle when an oxide film reaction surface control agent is used and when an oxide film reaction surface control agent is not used means the thin film deposition thickness (Å / cycle) per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated as an average deposition rate by measuring the final thickness of a thin film having a thickness of 3 to 30 nm under conditions of room temperature and pressure using spectroscopic ellipsometry, and then dividing the measured thickness by the total number of cycles.

[0132] In the formula 1, "when no oxide film reaction surface control agent was used" means that only a precursor compound is adsorbed on a substrate in a thin film deposition process to produce a thin film. A specific example of the method for forming an oxide film is that the step of adsorbing an oxide film reaction surface control agent and the step of purging unadsorbed oxide film reaction surface control agent are omitted to form an oxide film.

[0133] In the oxide film forming method, the residual halogen intensity (c / s) in the thin film, measured based on SIMS (secondary ion mass spectrometry), based on a thin film thickness of 100 Å, 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, and in a preferred embodiment, can be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within such ranges, the effect of preventing corrosion and deterioration is excellent.

[0134] In the present description, the purging rate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and further preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition (deposition) is performed in an atomic mono-layer or close to it, which is advantageous in terms of film quality.

[0135] The ALD (atomic layer deposition) process is highly 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.

[0136] The oxide film forming method may be performed at a deposition temperature in the range of, for example, 50 to 800°C, preferably 300 to 700°C, more preferably 400 to 650°C, more preferably 400 to 600°C, and even more preferably 450 to 600°C. Within this range, it is possible to realize the characteristics of the ALD process and grow a thin film with excellent film quality.

[0137] The oxide film forming method can be carried out at a deposition pressure in the range of, for example, 0.01 to 20 Torr, preferably 0.1 to 20 Torr, more preferably 0.1 to 10 Torr, and most preferably 0.3 to 7 Torr. Within this range, it is effective to obtain a thin film of uniform thickness.

[0138] In this description, deposition temperature and pressure can be measured as the temperature and pressure formed within a deposition chamber or as the temperature and pressure applied to a substrate within the deposition chamber.

[0139] The method for forming an oxide film may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the precursor compound into the chamber; and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the precursor compound into the chamber.

[0140] In addition, the present invention may include a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, the thin film manufacturing apparatus including an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transfer means for transferring the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second transfer means for transferring the vaporized thin film precursor to the ALD chamber. Here, the vaporizer and the transfer means are not particularly limited as long as they are vaporizers and transfer means commonly used in the technical field to which the present invention belongs.

[0141] As a specific example, the oxide film forming method will be described. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0142] The substrate may include a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0143] The substrate may further have a conductive layer or an insulating layer formed on an upper surface thereof.

[0144] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned oxide film reaction surface control agent and a precursor compound or a mixture thereof with a non-polar solvent are prepared.

[0145] The prepared oxide film reaction surface control agent is then injected into a vaporizer, converted into a vapor phase, and delivered to a deposition chamber to be adsorbed onto a substrate. The precursor compound / thin film forming composition is then purged to remove any unadsorbed oxide film reaction surface control agent.

[0146] Next, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (thin film forming composition) is injected into a vaporizer, converted into a vapor phase, delivered to a deposition chamber, and adsorbed onto a substrate, and unadsorbed precursor compound / thin film forming composition is purged.

[0147] In the present description, the steps of adsorbing the precursor compound onto a substrate and then purging to remove unadsorbed oxide film reaction surface control agent; and adsorbing the precursor compound onto a substrate and purging to remove unadsorbed precursor compound may be performed in a different order as necessary.

[0148] In this description, the method of delivering the oxide film reaction surface control agent, the precursor compound, and the precursor compound (thin film forming composition) to the deposition chamber may be, for example, a method of delivering a vaporized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC) or a method of delivering a liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System; LDS), and preferably, an LDS (liquid delivery) method is used.

[0149] Here, the transport gas or dilution gas for transporting the oxide film reaction surface control agent, the precursor compound, and the like 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.

[0150] In the present description, the purge gas may be, by way of example only, an inert gas, preferably the above-mentioned transport gas or dilution gas.

[0151] Next, 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 oxidizing agent reacts with the precursor compound adsorbed on the substrate to form an oxide film.

[0152] Preferably, the oxidant (reactive gas) is O2, O3, N2O, NO2, H2O, or a plasma of O2.

[0153] Next, the remaining unreacted reactant gas is purged with an inert gas, which removes not only the excess reactant gas but also the by-products that are produced.

[0154] As described above, the oxide film forming method has, as a unit cycle, for example, a step of applying an oxide film reaction surface control agent onto a substrate, a step of forming a shield for a precursor compound on the substrate, a step of purging unadsorbed oxide film reaction surface control agent, a step of adsorbing the precursor compound / thin film forming composition onto the substrate, a step of purging unadsorbed precursor compound / thin film forming composition, a step of supplying a reactive gas, and a step of purging residual reactive gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0155] In another example, the oxide film forming method may include a unit cycle including a step of adsorbing a precursor compound / a composition for forming a thin film on a substrate, a step of purging unadsorbed precursor compound / a composition for forming a thin film, a step of adsorbing an oxide film reaction surface control agent on a substrate, a step of purging unadsorbed oxide film reaction surface control agent, a step of supplying a reactive gas, and a step of purging remaining reactive gas, and the unit cycle may be repeated to form a thin film of a desired thickness.

[0156] 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 even more preferably 100 to 2,000 times. Within this range, the desired thin film properties can be effectively exhibited.

[0157] The present invention also provides a semiconductor substrate, which is manufactured by the method for forming an oxide film described herein. In this case, the step coverage and thickness uniformity of the thin film are excellent, and the thin film has excellent density and electrical properties.

[0158] The thin film (oxide film) may have a thickness of, for example, 0.1 to 20 nm, preferably 0.5 to 20 nm, more preferably 1.5 to 15 nm, and even more preferably 2 to 10 nm. Within this range, there is an effect of excellent thin film characteristics.

[0159] The thin film may have a carbon impurity content of preferably 5,000 counts / sec or less or 1 to 3,000 counts / sec, more preferably 10 to 1,000 counts / sec, and even more preferably 50 to 500 counts / sec. Within this range, there is an effect of reducing the thin film growth rate while maintaining excellent thin film properties.

[0160] 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 thin films with complex structures can be easily deposited on a substrate, and there is an advantage that the thin films can be applied to next-generation semiconductor devices.

[0161] The prepared thin film preferably has a thickness of 20 nm or less, a dielectric constant of 5 to 29 based on a thin film thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage rate of 90% or more. Within this range, the thin film has excellent performance as a dielectric film or a blocking film, but is not limited thereto.

[0162] The oxide film may have a multilayer structure of two or more layers, preferably two or three layers, as required. A specific example of the multilayer film having a two-layer structure may be a lower layer film-middle layer film structure, and a specific example of the multilayer film having a three-layer structure may be a lower layer film-overlying layer film-upper layer film structure.

[0163] As an example, the underlayer film may include 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.

[0164] The middle layer may, by way of example, comprise TixNy, preferably TN.

[0165] The upper layer film may include, for example, one or more selected from the group consisting of W and Mo.

[0166] 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.

[0167] 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 are possible within the scope and technical spirit of the present invention. It is of course understood that such changes and modifications fall within the scope of the appended claims.

[0168] [Example] <Examples 1 to 7 and Comparative Examples 1 to 10> The ALD deposition process was carried out according to the process shown in FIG. 1 using the components and process conditions shown in Table 1 below.

[0169] FIG. 1 is a schematic diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0170] Argon was flowed into the chamber at 5000 ml / min, and the pressure inside the vacuum pump was adjusted to 1.5 Torr to form a thin inert atmosphere.

[0171] The oxide film reaction surface control agent shown in Table 1 below was placed in a canister, and the partial pressure and temperature were adjusted to obtain the injection amount (mg / cycle). The canister was then injected into a deposition chamber with a substrate loaded therein for 1 second to coat the substrate, and the chamber was then purged for 10 seconds.

[0172] Next, the precursor compounds were placed in canisters and fed into the deposition chamber through a VFC (vapor flow controller) according to Table 1 below, and the chamber was purged for 10 seconds.

[0173] Next, the concentration of O3 in O2 as a reactive gas is 200 g / m 3 The mixture was placed in a deposition chamber so that the temperature was as shown in Table 1, and the chamber was purged for 10 seconds. During this process, the substrate on which the thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0174] This process was repeated 100 to 400 times to form a thin film of the self-limiting atomic layer having a thickness of 10 nm.

[0175] For each of the obtained thin films of Examples 1 to 7 and Comparative Examples 1 to 10, the deposition rate reduction rate (D / R reduction rate) and C impurity by SIMS (secondary ion mass spectrometry) were measured by the following method, and the results are shown in Table 1 below.

[0176] *Deposition rate reduction rate (D / R (dep. rate) reduction rate): This refers to the ratio of the deposition rate reduction after inserting the shield compared to the reduction rate (D / R) before the oxide film reaction surface control agent was added, and was calculated as a percentage using the measured A / cycle value for each.

[0177] Specifically, the reduction rate of the thin film growth rate was calculated by dividing the thickness of the thin film measured by an ellipsometer, which is a device that can measure optical properties such as the thickness and refractive index of a thin film by the number of cycles, and calculating the thickness of the thin film deposited (deposited) per cycle. Specifically, the calculation was performed using the following Equation 1.

[0178] [Formula 1] Deposition rate reduction rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0179] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. In the deposition of a thin film formed from a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any reaction surface control agent. DR f (final deposition rate) is the deposition rate of a thin film formed by adding an oxide film reaction surface control agent when carrying out the same process as above. Here, the deposition rate (DR) is a value measured at room temperature and pressure for a thin film having a thickness of 3 to 30 nm using an ellipsometer device, and is expressed in units of Å / cycle.)

[0180] *The non-uniformity was calculated by selecting the maximum and minimum thicknesses among the thicknesses of the thin film measured by the ellipsometer and using the following Equation 2, and the results are shown in Table 1. Specifically, the thickness was measured at four locations on the edges of the 300 mm wafer, north, south, east and west, and at one location in the center.

[0181] [Formula 2] Non-uniformity % = [{(Maximum thickness - Minimum thickness) / 2} x Average thickness] x 100

[0182] *SIMS (Secondary-ion mass spectrometry) C impurity: The thin film was dug in the axial direction by ion sputtering, and the C impurity counts in the surface layer of the substrate, where there is little contamination, and the sputtering time was 50 seconds were taken into consideration, and the C impurity value was confirmed on a SIMS (Secondary-ion mass spectrometry) graph.

[0183] *Step coverage (%): On a substrate having a complex structure with an aspect ratio of 22:1, thin films were deposited in accordance with Examples 1 to 7 and Comparative Examples 1 to 10. The thin films were horizontally cut at a position 100 nm downward from the top end (left side drawing) and at a position 100 nm upward from the bottom end (right side drawing). The step coverage (%) was measured using a TEM (transmission electron microscope) and calculated using the following formula 3.

[0184] [Formula 3] Step coverage (%) = (thickness deposited on the lower inner wall / thickness deposited on the upper inner wall) x 100

[0185] Specifically, a deposition process was performed using the application conditions of the diffusion improvement material on a substrate having 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 approximately 2000 nm. In order to check the uniformity of the thickness deposited inside the vertically formed via hole and the step coverage, a specimen was prepared by cutting horizontally at a position 100 nm downward from the upper end and a position 100 nm upward from the lower end. The results were measured using a transmission electron microscope (TEM), and are shown in Table 1 and Figures 2 to 3 below.

[0186] [Table 1]

[0187] In the above table, CpHf is an abbreviation for Tris(dimethylamido)cyclopentadienyl hafnium, and TMA is an abbreviation for trimethyl aluminum.

[0188] As shown in Table 1, it was confirmed that Examples 1 to 7, which used the oxide film reaction surface control agent and precursor compound according to the present invention, not only showed a significant improvement in the reduction rate of deposition rate compared to Comparative Example 1, which did not use these, but also had excellent impurity reduction properties and step coverage.

[0189] In addition, it was confirmed that Examples 1 to 7, which used the oxide film reaction surface control agent of the present invention, not only showed a significant improvement in the reduction rate of deposition rate compared to Comparative Examples 2 to 10, which used other types of agent deviating from the suitable type, but also had excellent impurity reduction properties and step coverage.

[0190] Specifically, the reduction rate of the deposition rate confirmed by the difference between the growth rates of Comparative Examples 2 to 10, which did not use the oxide film reaction surface control agent according to the present invention, was 9 to 38%. In contrast, it was confirmed that the reduction rate of the deposition rate confirmed by the difference between the growth rates of Examples 1 to 7, which used the oxide film reaction surface control agent according to the present invention, was excellent, being 53 to 89%.

[0191] It is expected that effective step coverage can be achieved even on pattern substrates having high aspect ratios.

[0192] In fact, as shown in Figures 2 and 3 below, the step coverage measured in Comparative Examples 2, 3, 4, 6, 8, and 10 was 23.6% or more and a maximum of 95%, while the step coverage measured in Examples 1, 3, 5, 6, and 7 of the present invention was excellent, with a minimum of 94.1% and a maximum of 110.5%, indicating that the use of an oxide film reaction surface control agent according to the present invention provides increased thickness at both the top and bottom.

Claims

1. An oxide film reaction surface control agent comprising one or more compounds selected from a cyclic compound having three or more element species having an unshared electron pair and a linear compound having three or more element species having an unshared electron pair, The cyclic compound having three or more elemental species having an unshared electron pair is a compound represented by the following chemical formula 1: The linear compound having three or more elemental species having an unshared electron pair is a compound represented by the following chemical formula 2: The oxide film reaction surface control agent controls a reaction surface, which is a surface of a substrate on which an oxide film is formed, and the oxide film is formed from one or more precursor compounds containing a central metal selected from among a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal. [Chemical formula 1] (In the above Chemical Formula 1, R' is hydrogen, 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; A is oxygen (O), sulfur (S), phosphorus (P), or nitrogen (N); and m is an integer of 0 to 2.) [Chemical formula 2] (In the above formula 2, R″ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkene group having 1 to 5 carbon atoms; The B is -OH, -OCH3, -OCH2CH3, -SH, -SCH3, or -SCH2CH3.

2. The oxide film reaction surface control agent according to claim 1, wherein the element species having an unshared electron pair is at least one selected from the group consisting of oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

3. 2. The oxide film reaction surface control agent according to claim 1, wherein the central metal is 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.

4. The oxide film reaction surface control agent according to claim 1, characterized in that the oxide film reaction surface control agent includes at least one compound selected from the compounds represented by the following chemical formulas 1-1 to 1-3 and 2-1 to 2-3. [Chemical formulas 1-1 to 1-3] [Chemical formulas 2-1 to 2-3]

5. A step of treating a surface of a substrate with the oxide film reaction surface control agent according to any one of claims 1 to 4; and sequentially injecting a precursor compound and a reaction gas into the chamber to form an oxide film on the surface of the loaded substrate; 1. A method for forming an oxide film, comprising:

6. 6. The method of claim 5, wherein the chamber is an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

7. 6. The method of claim 5, wherein the step of treating the surface of the substrate is performed by applying the oxide film reaction surface control agent to the substrate loaded in a chamber at a temperature of 20 to 800° C.

8. 6. The method of claim 5, wherein the oxide film reaction surface control agent and the precursor compound are transferred into the chamber by a VFC method, a DLI method or an LDS method.

9. 6. The method for forming an oxide film according to claim 5, wherein the oxide film is a silicon oxide film, a titanium oxide film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, an aluminum oxide film, a niobium oxide film, or a tellurium oxide film.

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