Oxide film reaction surface control agent, oxide film formation method using same, semiconductor substrate manufactured by the method, and semiconductor element

Abstract

The present invention relates to an oxide film reaction surface control agent, an oxide film formation method using the same, a semiconductor substrate manufactured by the method, and a semiconductor element, and provides a compound of a predetermined structure as an oxide film reaction surface control agent, forms a deposition layer of uniform thickness as a masking region on a substrate based on a difference in adsorption distribution of the oxide film reaction surface control agent, reduces a deposition rate of a thin film, and appropriately reduces a thin film growth rate, thereby being able to greatly improve step coverage and thickness uniformity of a thin film even when a thin film is formed on a substrate of a complex structure, and having an effect of reducing impurities.

Description

TECHNICAL FIELD

[0001] The present application relates to an oxide film reaction surface control agent, an oxide film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured by the method, and more particularly, to an oxide film reaction surface control agent that provides a predetermined structure as an oxide film reaction surface control agent, forms a deposition layer having a uniform thickness as a masking region on a substrate based on a difference in adsorption distribution, reduces a deposition rate of a thin film, and appropriately reduces a thin film growth rate, thereby greatly improving step coverage and thickness uniformity of a thin film even when a thin film is formed on a substrate having a complex structure, and greatly reducing impurities, an oxide film formation method using the same, and a semiconductor substrate manufactured by the method. BACKGROUND

[0002] As integration of a storage and a non-storage semiconductor device is improved, a fine structure of a substrate increasingly becomes complex.

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

[0004] Therefore, step coverage (step coverage ratio) defined by a ratio of thicknesses of deposition layers formed on an upper portion and a lower portion in a depth direction of a fine structure stays at about 90%, and it is increasingly difficult to express an electrical characteristic of a device, and thus, importance thereof is gradually increasing. The step coverage of 100% means that thicknesses of deposition layers formed on the upper portion and the lower portion of a fine structure are the same, and thus, a technology in which the step coverage is as close to 100% as possible needs to be developed.

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

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

[0007] As described above, in order to obtain excellent and uniform physical properties of a thin film deposited on a substrate, high step coverage of the thin film is essential, and therefore, an atomic layer deposition (ALD) process using surface reaction, rather than a chemical vapor deposition (CVD) process mainly using gas phase reaction, is used, but it is still difficult to achieve 100% step coverage.

[0008] When the deposition temperature is increased for the purpose of achieving 100% step coverage, there are difficulties in step coverage. First, in a deposition process composed of two kinds of precursors and reactants, an increase in deposition temperature not only causes a drastic increase in thin film growth rate (GPC), but even if an ALD process is used and performed at 300°C in order to alleviate the increase in GPC caused by the increase in deposition temperature, the deposition temperature increases during the process, and therefore, it cannot be considered a solution.

[0009] In addition, a high-temperature process is required to achieve a metal oxide film having excellent film quality in a semiconductor element. There have been reports of research results in which the atomic layer deposition temperature is increased to 400°C to reduce the concentration of carbon and hydrogen remaining in a thin film (see the paper J. Vac. Sci. Technol. A, 35 (2017) 01B130).

[0010] However, the higher the deposition temperature, the more difficult it is to ensure step coverage. First, in a deposition process composed of two kinds of precursors and reactants, an increase in deposition temperature causes a drastic increase in GPC (thin film growth rate). In addition, it can be confirmed that even if a conventional masking agent is used to alleviate the increase in GPC caused by the increase in deposition temperature, the GPC increases by about 10% at 300°C. That is, when deposition is performed at a temperature of 360°C or higher, it is difficult to expect the GPC reduction effect provided by the existing masking agent.

[0011] Therefore, there is a need to develop a thin film formation method that can effectively form a thin film having a complex structure even at a high temperature, has a low amount of impurities remaining, and greatly improves step coverage and thickness uniformity of the thin film, and a semiconductor substrate or the like manufactured by the method. SUMMARY

[0012] TECHNICAL PROBLEM

[0013] To solve the technical problems in the prior art as described above, the present application aims to provide an oxide film reaction surface control agent, an oxide film formation method using the same, and a semiconductor substrate manufactured by the method, which forms a deposition layer having a uniform thickness as a masking area for a thin film on a substrate based on the difference in adsorption distribution of the oxide film reaction surface control agent, reduces the deposition rate of the thin film, and appropriately reduces the thin film growth rate, thereby greatly improving the step coverage and the thickness uniformity of the thin film even when the thin film is formed on a substrate having a complex structure.

[0014] The present application aims to improve the crystallinity and oxidation ratio of a thin film, thereby improving the density and dielectric properties of the thin film.

[0015] The above and other objects of the present application can be achieved by the following.

[0016] Technical Solution

[0017] To achieve the above object, the present application provides an oxide film reaction surface control agent including one or more compounds selected from a cyclic compound having three or more element species having a lone pair of electrons and a linear compound having three or more element species having a lone pair of electrons, for controlling a reaction surface of an oxide film formed of a metal selected from one or more of a trivalent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal.

[0018] The lone pair of electrons can be one or more selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

[0019] The cyclic compound having three or more element species having a lone pair of electrons can be a compound represented by Chemical Formula 1.

[0020] Chemical Formula 1:

[0021]

[0022] In Chemical Formula 1, R' is 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,

[0023] A is oxygen (O), sulfur (S), phosphorus (P), or nitrogen (N),

[0024] m is an integer of 0 to 2.

[0025] The linear compound having three or more element species having a lone pair of electrons can be a compound represented by Chemical Formula 2.

[0026] Chemical Formula 2:

[0027]

[0028] In the Chemical Formula 2, R" is 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, and B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3.

[0029] The refractive index of the oxide film reaction surface control agent (measured at 20°C to 25°C) can be 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.

[0030] The oxide film reaction surface control agent can include one or more compounds selected from the group consisting of the compounds represented by Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3.

[0031] Chemical Formulae 1-1 to 1-3:

[0032]

[0033] Chemical Formulae 2-1 to 2-3:

[0034]

[0035] The reaction surface of an oxide film formed from a precursor compound can be controlled, and the metal is 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.

[0036] In addition, the present application provides an oxide film formation method including the steps of:

[0037] treating the surface of a substrate with the oxide film reaction surface control agent described above; and

[0038] For the treated substrate, a precursor compound and a reaction gas are sequentially injected into a chamber to form an oxide film on the surface of the loaded substrate.

[0039] The 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.

[0040] In the surface treatment step of the substrate, the oxide film reaction surface control agent can be applied to a substrate loaded in a chamber at 20°C to 800°C.

[0041] The oxide film reaction surface control agent and the precursor compound are delivered into the chamber by a vapor flow control (VFC) method, a direct liquid injection (DLI) method, or a liquid delivery system (LDS) method. The thin film can 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.

[0042] The reaction gas can include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0043] The oxide film can be a thin film in which one or two or more layers of a metal 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 are laminated.

[0044] The thin film can be used as a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a bulk oxide film, or a charge trap.

[0045] An oxide film formation method is provided, which includes the steps of:

[0046] (i) vaporizing the above-described oxide film reaction surface control agent to form a shielded region on the surface of a substrate loaded in a chamber;

[0047] (ii) performing a first purge of the inside of the chamber with a purge gas;

[0048] (iii) vaporizing a precursor compound and adsorbing it to a region other than the shielded region;

[0049] (iv) performing a second purge of the inside of the chamber with a purge gas;

[0050] (v) supplying a reaction gas to the inside of the chamber; and

[0051] (vi) performing a third purge of the inside of the chamber with a purge gas.

[0052] In the reaction surface activation step, a reaction surface-activated substrate can be produced by applying the oxide film reaction surface control agent to a substrate loaded in a chamber at 20°C to 800°C.

[0053] The precursor compound can be a precursor having a vapor pressure greater than 0.01 mTorr and less than or equal to 100 Torr at 25°C as a molecule formed from 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.

[0054] The method can further include a step of performing a post-plasma treatment after the precursor compound or the precursor compound gas is vaporized and injected.

[0055] The amount of the purge gas introduced into the interior of the chamber in the step (ii) and the step (iv) can be 10 to 100,000 times the volume of the oxidation film reaction surface control agent introduced.

[0056] The reaction gas is an oxidizing agent, and the reaction gas, the oxidation 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.

[0057] The substrate loaded in the chamber is heated to 100°C to 800°C, and the ratio of the oxidation film reaction surface control agent to the amount of the precursor compound introduced into the chamber (mg / cycle) can be 1:1 to 1:20.

[0058] In addition, the present application provides a semiconductor substrate including an oxidation film formed by the oxidation film formation method described above.

[0059] The oxidation film can be a multilayer structure of two or more layers.

[0060] In addition, the present application provides a semiconductor element including the semiconductor substrate described above.

[0061] 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.

[0062] Advantages

[0063] According to the present application, there is provided an oxide film reaction surface control agent which effectively shields adsorption on a substrate surface to reduce a reaction rate and appropriately reduces a film growth rate, thereby enabling improvement in step coverage even when a thin film is formed on a substrate having a complex structure.

[0064] In addition, when a thin film is formed, process by-products are more effectively reduced to prevent corrosion and deterioration, and the film quality is improved to improve the crystallinity of the thin film, thereby improving the electrical characteristics of the thin film.

[0065] In addition, when a thin film is formed, process by-products are reduced, and step coverage and film density can be improved, and further, an oxide film formation method using the same and a semiconductor substrate manufactured by the method are provided. BRIEF DESCRIPTION OF DRAWINGS

[0066] Figure 1 is a view which schematically shows a deposition process sequence of the present application as one cycle.

[0067] Figure 2 is a TEM photograph which photographs a deposition thickness at an upper portion (100 nm from the top) and a lower portion (100 nm from the bottom) of a cross section of an oxide film deposited according to Comparative Example 1 without using an oxide film reaction surface control agent and a deposition thickness at an upper portion (100 nm from the top) and a lower portion (100 nm from the bottom) of a cross section of an oxide film deposited using an oxide film reaction surface control agent.

[0068] Figure 3 is a TEM photograph which photographs a deposition thickness at an upper portion (100 nm from the top) and a lower portion (100 nm from the bottom) of a cross section of an oxide film deposited according to Comparative Example 1 without using an oxide film reaction surface control agent and a deposition thickness at an upper portion (100 nm from the top) and a lower portion (100 nm from the bottom) of a cross section of an oxide film deposited using an oxide film reaction surface control agent. DETAILED DESCRIPTION

[0069] Hereinafter, an oxide film reaction surface control agent of the present application, an oxide film formation method using the same, and a semiconductor substrate manufactured by the method will be described in detail.

[0070] In the present application, unless otherwise defined, the term "reaction surface control" means control of a surface of a reaction surface of a substrate used in a deposition process to adsorb a precursor compound to the surface of the substrate at a reduced reaction rate.

[0071] In the present application, unless otherwise defined, the term "masking" means not only reducing, preventing or blocking adsorption of a precursor compound for forming a thin film onto a substrate, but also reducing, preventing or blocking adsorption of a process by-product onto a substrate.

[0072] The inventors of the present application have confirmed that, by using a compound of a predetermined structure as an oxidation film reaction surface control agent for reducing the adsorption speed of a precursor compound (for forming an oxidation film on a substrate loaded in the inside of a chamber) onto a reaction surface for reaction, based on the difference in the adsorption distribution of the oxidation film reaction surface control agent, a deposition layer of uniform thickness is formed as a masking region that does not remain in a thin film, thereby greatly reducing the growth rate of a formed thin film while forming a relatively sparse thin film, and thus, even when applied to a substrate of complex structure at a high temperature, the uniformity of a thin film can be ensured, thereby greatly improving step coverage, and in particular, a relatively thin thickness can be deposited, and O, Si, metal, metal oxide and carbon residue, which have been difficult to reduce in the past, remaining as process by-products can be improved. Based on this, the oxidation film reaction surface control agent providing a masking region was researched, thereby completing the present application.

[0073] The oxidation film reaction surface control agent of the present application is used to control a reaction surface on which an oxidation film is to be formed on a substrate.

[0074] As an example, the thin film can be formed of a precursor selected from one or more 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 a masking region for an oxidation film, a nitride film, a metal film or a selective thin film thereof can be provided, in which case the effects to be achieved by the present application can be sufficiently obtained.

[0075] As a specific example, the thin film can have a film composition of 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.

[0076] The thin film can be used not only as a diffusion barrier film generally used in a semiconductor element, but also as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a bulk phase oxidation film or a charge trap.

[0077] In the present application, the precursor compound used to form the thin film is a molecule having one or more ligands including C, N, O, H, X (halogen), Cp (cyclopentadiene) with one or more central metal atoms (M) selected from one or more 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, which can be a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C.

[0078] As an example, the precursor compound can use a compound represented by Chemical Formula 3.

[0079] Chemical Formula 3:

[0080]

[0081] In 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, L1, L2, L3, and L4 are -H, -X, -R, -OR, -NR2, or Cp (cyclopentadiene), which can be the same as or different from each other, wherein -X is F, Cl, Br, or I, -R is C1 to C10 alkyl, C1 to C10 alkenyl, or C1 to C10 alkane, which can be linear or cyclic, and the L1, L2, L3, and L4 can be formed to be 2 to 6 depending on the oxidation valence of the central metal.

[0082] As an example, when the central metal is divalent, L1 and L2 can be bonded to the central metal as ligands, and when the central metal is hexavalent, L1, L2, L3, L4, L5, L6 can be bonded to the central metal, and the ligands corresponding to L1 to L6 can be the same as or different from each other.

[0083] The M can be a kind corresponding to a trivalent metal, a tetravalent metal, a pentavalent metal, or a hexavalent metal, and is preferably hafnium (Hf), zirconium (Zr), aluminum (Al), niobium (Nb), or tantalum (Ta), in which case the process by-product reduction effect is significant, the step coverage is excellent, and the thin film density improvement effect, the electrical characteristics, the insulation, and the dielectric characteristics of the thin film are more excellent.

[0084] The L1, L2, L3, and L4 are -R, -X, or Cp, which can be the same as or different from each other, wherein -R is C1 to C10 alkyl, C1 to C10 alkenyl, or C1 to C10 alkane, which can have a linear or cyclic structure.

[0085] In addition, L1, L2, L3, and L4 are -NR2 or Cp, which can be the same as or different from each other, wherein -R can be H, C1 to C10 alkyl, C1 to C10 alkenyl, C1 to C10 alkane, iPr, or tBu.

[0086] In addition, in the chemical formula 8, L1, L2, L3, and L4 are -H or -X, which can be the same as or different from each other, wherein -X can be F, Cl, Br, or I.

[0087] Specifically, the aluminum precursor compound can be, for example, Al(CH3)3, A1C14, or the like.

[0088] The hafnium precursor compound can be, for example, tris(dimethylamide) cyclopentadienyl hafnium (CpHf(NMe2)3), (methyl-3-cyclopentadienyl propylamino) bis(dimethylamino) hafnium (Cp(CH2)3NM3Hf(NMe2)2), or the like.

[0089] The oxide film reaction surface control agent of the present application can control in advance the reaction surface of the substrate on which the precursor compound is to be adsorbed, thereby reducing the speed of adsorbing the precursor compound on the substrate.

[0090] As an example, the shield region can be formed in the entire substrate or a part of the substrate on which the thin film is to be formed.

[0091] Further, when the total area of the entire substrate or a part of the substrate is set to 100%, as an example, the shield region can occupy an area of 10% to 95%, as a specific example, an area of 15% to 90%, preferably, an area of 20% to 85%, more preferably, an area of 30% to 80%, even more preferably, an area of 40% to 75%, further preferably, an area of 40% to 70%, and the unshield region can occupy the remaining area.

[0092] Further, when the total area of the entire substrate or a part of the substrate is set to 100%, as an example, the first shield region in the shield region can occupy an area of 10% to 95%, as a specific example, an area of 15% to 90%, preferably, an area of 20% to 85%, more preferably, an area of 30% to 80%, even more preferably, an area of 40% to 75%, further preferably, an area of 40% to 70%, the second shield region can occupy an area of 10% to 95% in the remaining area, as a specific example, an area of 15% to 90%, preferably, an area of 20% to 85%, more preferably, an area of 30% to 80%, even more preferably, an area of 40% to 75%, further preferably, an area of 40% to 70%, and the remaining area can be occupied by the unshield region.

[0093] The oxidation film reaction surface control agent can provide a controlled reaction surface to the surface of a substrate on which the above-mentioned thin film is to be formed.

[0094] The oxidation film reaction surface control agent can include a linear or cyclic saturated hydrocarbon or a linear saturated hydrocarbon containing three or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) and having a carbon atom number of 3 to 15, in which case, by forming a masking area that does not remain in the thin film when the thin film is formed, a side reaction can be suppressed while forming a relatively sparse thin film, and the thin 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, and when a metal oxide film is formed, a stoichiometric oxidation state is achieved, 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 greatly improved.

[0095] As a specific example, the oxidation film reaction surface control agent can have a structure in which nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) is independently contained at both ends of a central carbon atom to which oxygen is connected through a double bond, and thus, the process by-product reduction effect is significant, the step coverage is excellent, and the thin film density improvement effect and the electrical properties of the thin film are more excellent.

[0096] In the above-mentioned structure in which nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) is independently contained at both ends of a central carbon atom to which oxygen is connected through a double bond, unless specifically defined otherwise, the structure means a structure in which

[0097] As a specific example, the oxidation film reaction surface control agent can have a structure in which nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) is contained at one end of a central carbon atom to which oxygen is connected through a double bond and carbon (C) is contained at the other end, and thus, the process by-product reduction effect is significant, the step coverage is excellent, and the thin film density improvement effect and the electrical properties of the thin film are more excellent.

[0098] In the above-mentioned structure in which nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) is contained at one end of a central carbon atom to which oxygen is connected through a double bond and carbon (C) is contained at the other end, unless specifically defined otherwise, the structure means a structure in which

[0099] As a specific example, the oxide film reaction surface control agent includes one or more compounds selected from a cyclic compound having three or more element species having a lone pair of electrons and a linear compound having three or more element species having a lone pair of electrons, in which the reaction surface of an oxide film containing a metal selected from one or more of a trivalent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal is controlled, thereby suppressing a side reaction while forming a relatively sparse thin film, and adjusting a thin film growth rate to reduce a process by-product in the thin film, thereby reducing corrosion and deterioration, and improving crystallinity of the thin film, and when forming a metal oxide film, reaching a stoichiometric oxidation state, and even when forming a thin film on a substrate having a complex structure, step coverage and thickness uniformity of the thin film can be greatly improved.

[0100] The lone pair of electrons can be one or more selected from oxygen (O), sulfur (S), phosphorus (P), and nitrogen (N).

[0101] Preferably, the oxide film reaction surface control agent can be one or more selected from a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2, in which a shadow area that does not remain in a thin film can be formed when forming the thin film, a side reaction can be suppressed while forming a relatively sparse thin film, and a thin film growth rate can be adjusted to reduce a process by-product in the thin film, thereby reducing corrosion and deterioration, and improving crystallinity of the thin film, and even when forming a thin film on a substrate having a complex structure, step coverage and thickness uniformity of the thin film can be greatly improved.

[0102] Chemical Formula 1:

[0103]

[0104] In the Chemical Formula 1, R' is 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 (O), sulfur (S), phosphorus (P), or nitrogen (N), and m is an integer of 0 to 2.

[0105] The linear compound having three or more element species having a lone pair of electrons can be a compound represented by Chemical Formula 2.

[0106] Chemical Formula 2:

[0107]

[0108] In the Chemical Formula 2, R" is 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,

[0109] The B is -OH, -OCH3, -OCH2CH3, -CH2CH3, -SH, -SCH3, or -SCH2CH3.

[0110] These oxide film reaction surface control agents can be provided in a single or mixed gas phase, and thus, process by-product reduction effects are significant, step coverage is excellent, and film density improvement effects and film electrical characteristics are more excellent.

[0111] In the Chemical Formula 1, the R' is hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 1 to 5 carbon atoms, and preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 1 to 3 carbon atoms, and in this case, process by-product reduction effects are significant, step coverage is excellent, and film density improvement effects, film electrical characteristics, insulation, and dielectric characteristics are more excellent.

[0112] In the Chemical Formula 1, the A is oxygen (O) or sulfur (S), and preferably oxygen (O), and in this case, process by-product reduction effects are significant, step coverage is excellent, and film density improvement effects, film electrical characteristics, insulation, and dielectric characteristics are more excellent.

[0113] The m is an integer of 0 to 2, and preferably an integer of 1 to 2.

[0114] In the Chemical Formula 2, the R" is an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms, and in this case, process by-product reduction effects are significant, step coverage is excellent, and film density improvement effects and film electrical characteristics are more excellent.

[0115] In the Chemical Formula 2, the B is -OCH3, -OCH2CH3, -OCHCH3, -SH, -SCH3, or -SCH2CH3, and preferably -OCH3, -OCH2CH3, or -OCHCH3, and in this case, process by-product reduction effects are significant, step coverage is excellent, and film density improvement effects and film electrical characteristics are more excellent.

[0116] As a specific example, the oxide film reaction surface control agent can include one or more compounds selected from the group consisting of Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3, and in this case, effects of adjusting a film growth rate by providing a film masking area are significant, process by-product removal effects are also significant, step coverage improvement and film quality improvement effects are excellent.

[0117] Chemical Formulae 1-1 to 1-3:

[0118]

[0119] Chemical Formula 2-1 to Chemical Formula 2-3:

[0120]

[0121] When the oxide film reaction surface control agent is used, based on the difference in the adsorption distribution of the activation agent having the above structure, a deposition layer of uniform thickness is formed as a masking area that does not remain in the thin film, thereby greatly reducing the growth rate of the formed thin film while forming a relatively sparse thin film, and thus, even when applied to a substrate having a complex structure, the uniformity of the thin film can be ensured, thereby greatly improving the step coverage, and in particular, the thin film can be deposited with a thinner thickness, and the O, Si, metal, metal oxide, and carbon residue amount that are difficult to reduce in the past can be improved.

[0122] The refractive index of the oxide film reaction surface control agent can be 1.365 to 1.48, 1.366 to 1.393, or 1.367 to 1.391. At this time, the reaction surface on which the oxide film is to be formed on the surface of the substrate is controlled in advance to improve the reaction speed, and even when a thin film is formed on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film are greatly improved, and the adsorption of the thin film precursor and the process by-products are prevented to effectively protect the surface of the substrate and effectively remove the process by-products.

[0123] The reaction gas can include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0124] The oxide film can be a thin film in which one or more layers of a metal 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 are stacked.

[0125] The oxide film reaction surface control agent can form a masking area for a thin film.

[0126] The masking area for a thin film does not remain in the thin film.

[0127] At this time, unless otherwise defined, non-residual means that, when analyzing the components 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 measured in a manner of digging into the substrate in a depth direction, when considering the increase / decrease rate of C, N, Si, halogen impurities before and after using the oxide film reaction surface control agent under the same deposition conditions, the signal intensity increase / decrease rate of each element species is preferably 5% or less.

[0128] As an example, the content of the halogen compound in the oxide film can be 100 ppm or less.

[0129] The oxide film can be used as a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a bulk oxide film, or a charge trap, but is not limited thereto.

[0130] Preferably, the oxide film reaction surface control agent and the precursor compound can 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 can remain in the thin film, or a side reaction with the precursor or the reactant can occur, and thus a substance of 99% or more should be used as much as possible.

[0131] Preferably, the oxide film reaction surface control agent is used in an atomic layer deposition (ALD) process, at which time the surface of the substrate is effectively protected as the oxide film reaction surface control agent without hindering the adsorption of the precursor compound, and has the advantage of effectively removing process by-products.

[0132] Preferably, the oxide film reaction surface control agent is a liquid at room temperature (22°C), and the density can be 0.8 to 2.5 g / cm 3 or 0.8 to 1.5 g / cm 3 , and the vapor pressure (20°C) can be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, a shadow area is effectively formed, and has excellent effects of step coverage, thickness uniformity of the thin film, and improvement of film quality.

[0133] More preferably, the density of the oxide film reaction surface control agent can be 0.75 to 2.0 g / cm 3or 0.8 to 1.3 g / cm 3 The vapor pressure (20°C) can be 1 to 260 mmHg, and within this range, the shadowing region is effectively formed, and the step coverage, the thickness uniformity of the film, and the film quality are improved.

[0134] The oxide film forming method of the present application includes the steps of: treating the 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 for the treated substrate to form an oxide film on the surface of the loaded substrate, at this time, forming a shadowing region for a thin film on the substrate to reduce the deposition rate of the thin film and appropriately reduce the film growth rate, thereby greatly improving the step coverage and the thickness uniformity of the thin film even when forming a thin film on a substrate with a complex structure.

[0135] In the step of treating the surface of a substrate with the oxide film reaction surface control agent, the feeding time (sec) of the oxide film reaction surface control agent to the surface of the substrate per cycle is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and further preferably 0.05 to 5 seconds, and within this range, the film growth rate is low and the step coverage and economy are excellent.

[0136] In the present application, the feeding time of the precursor compound is 0.1 to 500 mg / cycle based on the flow rate of the chamber volume of 15 to 20 L, and more specifically, 0.8 to 200 mg / cycle based on the flow rate of the chamber volume of 18 L.

[0137] As a preferred embodiment, the oxide film forming method can include the steps of: (i) vaporizing the oxide film reaction surface control agent to treat the surface of a substrate loaded in a chamber; (ii) first purging the inside of the chamber with a purge gas; (iii) vaporizing a precursor compound and adsorbing it to the surface of a substrate loaded in the chamber; (iv) second purging the inside of the chamber with a purge gas; (v) supplying a reaction gas to the inside of the chamber; (vi) third purging the inside of the chamber with a purge gas.

[0138] At this time, the steps (i) to (vi) can be taken as a unit cycle, and the cycle can be repeatedly performed until a thin film of a desired thickness is obtained, and when the oxidized film reaction surface control agent of the present application is introduced before the precursor compound in one cycle and adsorbed to the substrate in this manner, even if the deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, and the generated process by-products can be effectively removed to reduce the resistivity of the thin film, and the step coverage can be greatly improved.

[0139] As another preferred embodiment, in the reaction surface control step, the substrate whose reaction surface is controlled can be produced by applying the oxidized film reaction surface control agent to a substrate loaded in a chamber at 20°C to 800°C.

[0140] As a preferred example, the oxidized film formation method of the present application can introduce the oxidized film reaction surface control agent of the present application before the precursor compound in one cycle to activate the surface of the substrate, and then introduce the precursor compound and adsorb it to the substrate, at this time, even if the thin film is deposited at a high temperature, the thin film growth rate can be appropriately reduced, thereby greatly reducing the process by-products, greatly improving the step coverage, and increasing the crystallinity of the thin film to reduce the resistivity of the thin film, and even if it is applied to a semiconductor element with a large aspect ratio, the thickness uniformity of the thin film can be greatly improved to ensure the reliability of the semiconductor element.

[0141] As an example, in the oxidized film formation method, when the precursor compound is deposited before or after the deposition of the precursor compound, the number of repetitions of the unit cycle performed as needed 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, and within this range, a desired thickness of the thin film can be obtained, and the effects to be achieved by the present application can be sufficiently obtained.

[0142] The precursor compound is a molecule having one or more ligands including C, N, O, H, X (halogen), and Cp (cyclopentadiene) with 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 as a central metal atom (M), and can be a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C, at this time, even if natural oxidation occurs, the effect of forming a shadow area based on the above oxidized film reaction surface control agent can be maximized.

[0143] In the present application, as an example, the chamber can be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0144] The thin film can 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.

[0145] In the present application, the following step can be included: after the precursor compound or the precursor compound gas is vaporized and injected, plasma post-treatment is performed, at which time the growth rate of the thin film can be improved and process by-products can be reduced.

[0146] When the oxide film reaction surface control agent is adsorbed first, the precursor compound is adsorbed, and then the precursor compound is adsorbed on the substrate, the amount of purge gas introduced into the interior of the chamber in the step of purging the unadsorbed oxide film reaction surface control agent can be sufficient to remove the unadsorbed oxide film reaction surface control agent, and as an example, 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 unadsorbed oxide film reaction surface control agent can be sufficiently removed, a uniform thin film can be formed, and deterioration of the film quality can be prevented. The amounts of the purge gas and the oxide film reaction surface control agent introduced are each based on one cycle, and the volume of the oxide film reaction surface control agent represents the volume of the vaporized oxide film reaction surface control agent vapor.

[0147] As a specific example, when the injection amount of the oxide film reaction surface control agent is set to 200 seem, and the flow rate of the purge gas in the step of purging the unadsorbed oxide film reaction surface control agent is set to 5000 seem, the injection amount of the purge gas is 25 times the injection amount of the oxide film reaction surface control agent.

[0148] In addition, in the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the interior of the chamber can be sufficient to remove the unadsorbed precursor compound, and as an example, can be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, the volume of the precursor compound introduced into the interior of the chamber. Within this range, the unadsorbed precursor compound can be sufficiently removed, a uniform thin film can be formed, and deterioration of the film quality can be prevented. The amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound represents the volume of the vaporized precursor compound vapor.

[0149] Further, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas supplied into the interior of the chamber can be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the reaction gas supplied into the interior of the chamber, in which range the desired effect can be sufficiently obtained. Here, the amounts of the purge gas and the reaction gas are each based on one cycle.

[0150] Preferably, the precursor compound and the precursor compound can be delivered into the chamber by a VFC method, a DLI method, or an LDS method, and more preferably, can be delivered into the chamber by an LDS method.

[0151] The substrate loaded in the chamber can be heated, for example, to 100 to 650°C, and specifically, for example, to 150 to 550°C, and the oxide film reaction surface control agent or the precursor compound can be injected onto the substrate in an unheated or heated state, and depending on the deposition efficiency, heating can be performed in the deposition process after injection in an unheated state. For example, the injection onto the substrate can be performed at 100 to 650°C in 1 to 20 seconds.

[0152] Preferably, the ratio of the amounts of the precursor compound and the oxide film reaction surface control agent supplied into the chamber (mg / cycle) can be 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and further preferably 1:2.5 to 1:10, in which range the step coverage improvement effect and the process by-product reduction effect are remarkable.

[0153] For example, in the oxide film formation method, when the oxide film reaction surface control agent and the precursor compound are used, the deposition rate reduction rate represented by Mathematical Formula 1 is 45% or more, and specifically, for example, can be 48% or more, and preferably 52% or more. In this case, the oxide film reaction surface control agent having the above structure is used to form a deposition layer having a uniform thickness on a thin film, thereby forming a relatively sparse thin film while greatly reducing the growth rate of the formed thin film, and thus, even when applied to a substrate having a complex structure at a high temperature, the uniformity of the thin film can be ensured, thereby greatly improving the step coverage, and in particular, the thin film can be deposited at a relatively thin thickness, and the O, Si, metal, metal oxide, and carbon residue amount, which are difficult to reduce in the past, can be improved.

[0154] Mathematical Formula 1:

[0155] Deposition rate reduction rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0156] In this formula, DR (Deposition rate) ) is the rate of thin film deposition. During the deposition of a thin film formed from precursors and reactants, DR... i Initial deposition rate (DR) is the deposition rate at which a thin film is formed without the addition of reactive surface control agents. f The final deposition rate (DR) is the deposition rate of the thin film formed during the above process by adding an oxide film reaction surface control agent. The deposition rate (DR) is measured using an ellipsometry at room temperature and pressure for thin films with a thickness of 3–30 nm, and the unit used is 100 nm.

[0157] In the mathematical formula 1, the film growth rate per cycle, with or without the use of an oxide film reaction surface control agent, represents the film deposition thickness per cycle. That is, the deposition rate, as an example, can be the average deposition rate obtained by measuring the final thickness of a film with a thickness of 3 to 30 nm using an ellipsometry under normal temperature and pressure conditions and then dividing it by the total number of cycles.

[0158] In the mathematical formula 1, "when no oxide film reaction surface control agent is used" means that the thin film is manufactured in the thin film deposition process by adsorbing only the precursor compound on the substrate. As a specific example, it means that the oxide film is formed by omitting the steps of adsorbing the oxide film reaction surface control agent and purging the unadsorbed oxide film reaction surface control agent in the oxide film formation method.

[0159] The oxide film formation method, measured using SIMS, has a film thickness of [missing information]. The residual halogen strength (c / s) in the film is 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. As a preferred embodiment, it can be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and deterioration is excellent.

[0160] In the present application, the purge is preferably 1,000 to 50,000 seem (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 seem, and even more preferably 2,500 to 15,000 seem, in which range the thin film growth rate per cycle is properly controlled and deposition is performed in a single atomic mono-layer or in a manner close thereto, and thus, is advantageous in terms of film quality.

[0161] The ALD (Atomic Layer Deposition process) is very advantageous in manufacturing an integrated circuit (IC) requiring a high aspect ratio, and in particular, has advantages such as excellent conformality, uniformity, and precise thickness control based on a self-limiting thin film growth mechanism.

[0162] As an example, the oxide film forming method can be performed at a deposition temperature in the range of 50°C to 800°C, preferably in the range of 300°C to 700°C, more preferably in the range of 400°C to 650°C, even more preferably in the range of 400°C to 600°C, and further preferably in the range of 450°C to 600°C, in which range there is an effect of realizing an ALD process characteristic and growing a thin film having excellent film quality.

[0163] As an example, the oxide film forming method can be performed at a deposition pressure in the range of 0.01 to 20 Torr, preferably in the range of 0.1 to 20 Torr, more preferably in the range of 0.1 to 10 Torr, and most preferably in the range of 0.3 to 7 Torr, in which range there is an effect of obtaining a thin film having uniform thickness.

[0164] In the present application, the deposition temperature and the deposition pressure can be measured by the temperature and the pressure formed in the deposition chamber or by the temperature and the pressure applied to the substrate in the deposition chamber.

[0165] Preferably, the oxide film forming method can include the steps of increasing the temperature in the chamber to the deposition temperature before the precursor compound is introduced into the chamber, and / or injecting an inert gas into the chamber to perform a purge before the precursor compound is introduced into the chamber.

[0166] In addition, in the present application, a thin film manufacturing apparatus capable of implementing the thin film manufacturing method can include an ALD chamber, a first vaporizer vaporizing a precursor compound, a first delivery unit delivering the vaporized precursor compound into the ALD chamber, a second vaporizer vaporizing a thin film precursor, and a second delivery unit delivering the vaporized thin film precursor into the ALD chamber. Here, the vaporizers and the delivery units can be those conventionally used in the art.

[0167] As a specific example, the thin film forming method is described as follows. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of performing atomic layer deposition.

[0168] The substrate can include a semiconductor substrate such as a silicon substrate, a silicon oxide substrate, etc.

[0169] The substrate can further include an electrically conductive layer or an insulating layer formed on an upper portion thereof.

[0170] The above-described oxide film reaction surface control agent and the precursor compound or a mixture thereof with a non-polar solvent are prepared separately to deposit a thin film on the substrate placed in the deposition chamber.

[0171] After the prepared oxide film reaction surface control agent is injected into a vaporizer and changed into a vapor phase, it is delivered into the deposition chamber and adsorbed on the substrate, and then purging is performed to remove the oxide film reaction surface control agent that is not adsorbed.

[0172] Next, after the prepared precursor compound or a mixture thereof with a non-polar solvent (thin film forming composition) is injected into a vaporizer and changed into a vapor phase, it is delivered into the deposition chamber and adsorbed on the substrate, and then purging is performed on the precursor compound / thin film forming composition that is not adsorbed.

[0173] In the present application, the order of the process of purging after the adsorption of the precursor compound on the substrate to remove the oxide film reaction surface control agent that is not adsorbed and the process of purging after the adsorption of the precursor compound on the substrate to remove the precursor compound that is not adsorbed can be changed as needed.

[0174] In the present application, as an example, a method of delivering a volatile gas using a vapor flow control (VFC) method or a method of delivering a liquid using a liquid delivery system (LDS) can be used as a method of delivering the oxidation film reaction surface control agent, the precursor compound, and the precursor compound (thin film forming composition) and the like to the deposition chamber, and preferably, the LDS method is used.

[0175] At this time, as a carrier gas or a dilution gas for delivering the oxidation film reaction surface control agent, the precursor compound, and the precursor compound (thin film forming composition) and the like to the substrate, one or more than two kinds of mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but is not limited thereto.

[0176] In the present application, as an example, an inert gas can be used as a purge gas, and preferably, the carrier gas or the dilution gas can be used.

[0177] Next, a reaction gas is supplied. The reaction gas can be any reaction gas conventionally used in the art, and preferably, can include a nitriding agent. The oxidation agent reacts with the precursor compound adsorbed on the substrate to form an oxidation film.

[0178] Preferably, the oxidation agent (reaction gas) is O2, O3, N2O, NO2, H2O, or O2 plasma.

[0179] Next, an inert gas is used to purge the remaining reaction gas that has not reacted. Thereby, not only excess reaction gas can be removed, but also by-products generated can be removed together.

[0180] As described above, as an example, the oxidation film forming method can repeat a unit cycle including a step of treating the substrate using the oxidation film reaction surface control agent; a step of masking the precursor compound on the substrate; a step of purging the oxidation film reaction surface control agent that has not been adsorbed; a step of adsorbing the precursor compound / thin film forming composition on the substrate; a step of purging the precursor compound / thin film forming composition that has not been adsorbed; a step of supplying a reaction gas; and a step of purging the remaining reaction gas, to form a thin film of a desired thickness.

[0181] As another example, the oxide film forming method can repeat, as a unit cycle, a step of adsorbing a precursor compound / thin film forming composition onto a substrate; a step of purging the precursor compound / thin film forming composition that is not adsorbed; a step of adsorbing an oxide film reaction surface control agent onto the substrate; a step of purging the oxide film reaction surface control agent that is not adsorbed; a step of supplying a reaction gas; and a step of purging the remaining reaction gas, to form a thin film of a desired thickness.

[0182] As an example, the number of repetitions of the unit cycle can be 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, in which range there is an effect of expressing desired thin film characteristics well.

[0183] The present application also provides a semiconductor substrate manufactured by the oxide film forming method of the present application, in which case the step coverage of the thin film and the thickness uniformity of the thin film are excellent, and the density and electrical characteristics of the thin film are excellent.

[0184] As an example, the thickness of the thin film (oxide film) can be 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, in which range there is an effect of excellent thin film characteristics.

[0185] The carbon impurity content of the thin film can be 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, in which range there is an effect of excellent thin film characteristics and reduced thin film growth rate.

[0186] As an example, the step coverage of the thin film can be 90% or more, preferably 92% or more, and more preferably 95% or more, in which range even a thin film with a complex structure can be easily deposited on a substrate, and thus there is an advantage of being applicable to next-generation semiconductor devices.

[0187] Preferably, the thin film manufactured 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 of 90% or more, in which range there is an effect of excellent performance as a dielectric film or barrier film, but not limited thereto.

[0188] As an example, the oxide film can be a multilayer structure of two or more layers, preferably, a multilayer structure of two or three layers, as needed. As a specific example, the multilayer film of two layers can be a structure of a lower layer film - middle layer film, and as a specific example, the multilayer film of three layers can be a structure of a lower layer film - middle layer film - upper layer film.

[0189] As an example, the lower layer film can contain one or more selected from Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, TiO2.

[0190] As an example, the middle layer film can contain Ti x N y , preferably, TN.

[0191] As an example, the upper layer film can contain one or more selected from W, Mo.

[0192] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitor, DRAM trench capacitor, 3D Gate-All-Around (GAA) or 3D NAND flash.

[0193] Hereinafter, preferred embodiments and drawings are presented to help understand the present application, and those skilled in the art will understand that the following embodiments and drawings are only for illustrating the present application, and various changes and modifications can be made within the scope and technical idea of the present application, and these changes and modifications fall within the scope of the appended claims.

[0194] [Embodiments]

[0195] Examples 1 to 7, Comparative Examples 1 to 10

[0196] An ALD deposition process was performed according to a process shown in Figure 1 using the components and process conditions shown in Table 1.

[0197] Figure 1 is a figure schematically showing a sequence of the deposition process of the present application in one cycle.

[0198] An argon gas was flowed into the inside of the chamber at 5000 mL / min, and the pressure in the chamber was made 1.5 Torr by a vacuum pump to form a rarefied inert atmosphere.

[0199] The oxidation film reaction surface control agent shown in Table 1 was charged into a tank and the partial pressure and temperature were adjusted to achieve the injection amount (mg / cycle), and then the deposition chamber loaded with the substrate was introduced for 1 second to coat the substrate, after which the chamber was purged for 10 seconds.

[0200] Next, the precursor compound was charged into a tank and introduced into the deposition chamber through a vapor flow controller (VFC) as shown in Table 1, and then the chamber was purged for 10 seconds.

[0201] Then, as the reaction gas, the concentration of O3 in O2 was made 200 g / m 3 and introduced into the deposition chamber as shown in Table 1, and then the chamber was purged for 10 seconds. At this time, the substrate to be formed with a thin film was heated at the temperature conditions shown in Table 1.

[0202] This process was repeated 100 to 400 times to form a self-limiting atomic layer thin film having a thickness of 10 nm.

[0203] The deposition rate reduction rate (D / R reduction rate) and the SIMS C impurity of each thin film obtained in Examples 1 to 7 and Comparative Examples 1 to 10 were measured by the following method and shown in Table 1.

[0204] * Deposition rate reduction rate (D / R (dep.rate) reduction rate): indicates the proportion of the reduction in the deposition rate after the introduction of the oxidation film reaction surface control agent compared to the D / R before the introduction of the shielding agent, and is calculated as a percentage using the D / R values measured respectively.

[0205] Specifically, the thickness of the thin film measured using an ellipsometer, which is a device capable of measuring optical characteristics such as the thickness or refractive index of a manufactured thin film using the polarization characteristics of light, was divided by the cycle number to calculate the thickness of the thin film deposited per cycle, thereby calculating the reduction rate of the thin film growth rate. Specifically, the calculation was performed using Mathematical Formula 1.

[0206] Mathematical Formula 1:

[0207] Deposition rate reduction rate = [{(DR i ) - (DR f )} / (DR i )] x 100

[0208] ​In the formula, DR (Deposition rate) is the speed of thin film deposition. When a thin film is formed from a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of a thin film formed without the use of a reaction surface control agent. DR f (final deposition rate) is the deposition rate of a thin film formed using an oxide film reaction surface control agent in the process described above. Here, the deposition rate (DR) is the value of a thin film having a thickness of 3 to 30 nm measured using an ellipsometer under normal temperature and pressure, and the unit used is

[0209] *Non-uniformity: The maximum thickness and the minimum thickness of the thickness of a thin film measured using the ellipsometer were selected, and the result calculated using Mathematical Formula 2 is shown in Table 1. Specifically, the thickness of the east, west, south, north, and center portions of a 300 mm wafer was measured.

[0210] Mathematical Formula 2:

[0211] Non-uniformity % = [{(maximum thickness - minimum thickness) / 2} x average thickness] x 100

[0212] *SIMS (Secondary-ion mass spectrometry) C impurity: The C impurity value was confirmed in a SIMS graph using ion sputtering to dig into a thin film along the axial direction, and considering the C impurity content (counts) at a sputter time of 50 seconds at which contamination at the skin layer of a substrate was less.

[0213] *Step coverage (%): TEM of a sample was measured, and calculation was performed using Mathematical Formula 3, wherein the sample was a thin film deposited on a complex substrate having an aspect ratio of 22:1 by Examples 1 to 7 and Comparative Examples 1 to 10, and was horizontally cut at 100 nm from the upper portion to the lower portion (left side drawing) and from the lower portion to the upper portion (right side drawing).

[0214] Mathematical Formula 3:

[0215] Step coverage (%) = (thickness deposited on the lower inner wall / thickness deposited on the upper inner wall) x 100

[0216] ​Specifically, for a substrate having a complex structure with an upper diameter of 90 nm, a lower diameter of 65 nm, a depth of the via of about 2000 nm, and an aspect ratio of 22:1, after the deposition process was performed using the diffusion improving substance application conditions, a sample was manufactured by horizontally cutting 100 nm from the upper portion and 100 nm from the lower portion, and measured using a transmission electron microscope (TEM) to confirm the thickness uniformity and step coverage of the deposition inside the vertically formed via, and shown in Table 1, Figures 2 to 3

[0217] Table 1:

[0218]

[0219]

[0220]

[0221] In the table, CpHf is a short name for tris(dimethylamido)cyclopentadienyl hafnium, and TMA is a short name for trimethyl aluminum.

[0222] As shown in Table 1, it can be confirmed that Examples 1 to 7 using the oxide film reaction surface control agent and the precursor compound of the present application have not only a remarkable improvement in the deposition rate reduction, but also excellent impurity reduction characteristics and step coverage, compared to Comparative Example 1 not using them.

[0223] In addition, it can be confirmed that Examples 1 to 7 using the oxide film reaction surface control agent of the present application have not only a remarkable improvement in the deposition rate reduction, but also excellent impurity reduction characteristics and step coverage, compared to Comparative Examples 2 to 10 using other kinds than the appropriate kind.

[0224] Specifically, the deposition rate reduction confirmed by the difference in growth rate of Comparative Examples 2 to 10 not using the oxide film reaction surface control agent of the present application is 9% to 38%, whereas the deposition rate reduction confirmed by the difference in growth rate of Examples 1 to 7 using the oxide film reaction surface control agent of the present application is 53% to 89%, which is very excellent.

[0225] Thus, it is expected that effective step coverage can also be achieved on a pattern substrate having a high aspect ratio.

[0226] In fact, as Figures 2 to 3 ​As shown, it can be confirmed that the step coverage measured according to Comparative Examples 2, 3, 4, 6, 8, and 10 is 23.6% or more, and the maximum is 95%, while the step coverage measured according to Examples 1, 3, 5, 6, and 7 of the present application is the minimum of 94.1%, and the maximum is 110.5%, which is excellent, and thus it can be known that the upper and lower portions can provide increased thickness when the oxidation film reaction surface control agent according to the present application is used.

Claims

1. Use of one or more compounds represented by Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3 as an oxide film reaction surface control agent in an atomic layer deposition process for pretreating a substrate surface on which an oxide film is to be formed on a semiconductor substrate having an aspect ratio of 20:1 or more, characterized in that the compound includes one or more compounds selected from a cyclic compound having three or more element species having a lone pair of electrons and a linear compound having three or more element species having a lone pair of electrons, the oxide film being formed from one or more precursor compounds selected from a trivalent metal, a tetravalent metal, a pentavalent metal, and a hexavalent metal, wherein the cyclic compound having three or more element species having a lone pair of electrons is a compound represented by Chemical Formulae 1-1 to 1-3, Chemical Formulae 1-1 to 1-3: wherein the linear compound having three or more element species having a lone pair of electrons is a compound represented by Chemical Formulae 2-1 to 2-3, Chemical Formulae 2-1 to 2-3:

2. The use of one or more compounds represented by Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3 as an oxide film reaction surface control agent in an atomic layer deposition process according to claim 1, characterized in that the oxide film reaction surface control agent has a refractive index of 1.365 to 1.

48.

3. The use of one or more compounds represented by Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3 as an oxide film reaction surface control agent in an atomic layer deposition process according to claim 1, characterized in that the oxide film reaction surface control agent controls the reaction surface of an oxide film formed from a precursor compound, the metal being one or more selected from Al, Ti, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ru, Rh, In, Sn, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd. including the steps of: treating the surface of a substrate loaded in a chamber with an oxide film reaction surface control agent; purging the inside of the chamber with a purge gas; and 。 sequentially injecting a precursor compound and a reaction gas into the chamber for each substrate to form an oxide film on the surface of the loaded substrate, wherein the oxide film reaction surface control agent includes one or more compounds represented by Chemical Formulae 1-1 to 1-3 and Chemical Formulae 2-1 to 2-3, Chemical Formulae 1-1 to 1-3: Chemical Formulae 2-1 to 2-3:

4. An oxide film forming method characterized by comprising: the substrate having an aspect ratio of 20:1 or more, and the oxide film being 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.

5. The oxide film formation method according to claim 4, characterized in that ​ ​ ​ ​ ​ ​ ​ ​ The chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, or a plasma enhanced chemical vapor deposition (PECVD) chamber.

6. The oxide film formation method according to claim 4, wherein In the surface treatment step of the substrate, the oxide film reaction surface control agent is applied to a substrate loaded in a chamber at 20°C to 800°C.

7. The oxide film formation method according to claim 4, wherein The oxide film reaction surface control agent and the precursor compound are delivered into the chamber by a vapor flow control (VFC) method, a direct liquid injection (DLI) method, or a liquid delivery system (LDS) method.

8. A semiconductor substrate, comprising an oxide film formed by the oxide film formation method according to claim 4, wherein The semiconductor substrate has an aspect ratio of 20:1 or more, and 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.

9. The semiconductor substrate according to claim 8, wherein The oxide film has a multilayer structure of two or more layers.

10. A semiconductor element, comprising the semiconductor substrate according to claim 8. ​ ​

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