Thin film shielding agent, thin film forming method using the same, semiconductor substrate and semiconductor device manufactured by the same

Abstract

The present invention relates to a thin film shielding agent, a thin film forming composition containing the same, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. By applying the thin film shielding agent, the reaction rate can be improved and the thin film growth rate can be appropriately reduced, so that even when a thin film is formed on a substrate having a complex structure under high temperature conditions, step coverage and thin film thickness uniformity can be significantly improved to form a seamless thin film, and impurities can be reduced to improve film quality.

Description

[Technical field]

[0001] The present invention relates to a thin film shielding agent, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. More particularly, the present invention relates to a thin film shielding agent that provides strong and stable physical or chemical adsorption to the surface of a deposition layer on a substrate surface, thereby significantly improving step coverage and thin film thickness uniformity to provide a seamless thin film even when a thin film is formed on a substrate having a complex structure under high temperature conditions, and that significantly reduces impurities and improves film quality, a thin film forming method using the same, and a semiconductor substrate manufactured thereby. [Background technology]

[0002] Increasing integration density of memory and non-memory semiconductor devices is leading to increasingly complex substrate topologies.

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

[0004] As a result, step coverage, which limits the thickness ratio of the deposition layer formed on the top and bottom of the microstructure in the depth direction, remains at a level of 90%, and the importance of this is increasing as it becomes increasingly difficult to express the electrical characteristics of the device. Since 100% step coverage means that the thickness of the deposition layer formed on the top and bottom of the microstructure is the same, it is necessary to develop technology that can achieve step coverage as close to 100% as possible.

[0005] Taking the example of metal NAND word lines, when a very narrow gap (trench) is filled, the metal content that accumulates at the top and bottom of the gap can differ. If the metal content accumulates predominantly at the top, there is concern that this can lead to seam defects, in which empty space is created inside the gap.

[0006] In order to achieve a step coverage of nearly 100%, which is a variable that determines whether the thickness of the atomic layers deposited on the top and bottom of a pattern are the same, it is necessary to create a difference in the adsorption density of the shielding agent to the precursor compound so that the precursor compound occupies more of the areas where it should be adsorbed at the top of the pattern and occupies less of the areas where it should be adsorbed at the top of the pattern as it moves toward the bottom.

[0007] On the other hand, in order to realize excellent film quality, it is necessary to overcome the problem that it becomes difficult to adsorb the screening agent onto the substrate as the deposition temperature increases.

[0008] As a specific example, according to Korean Patent Publication No. 2021-0059332, which uses ether as a shielding material, instead of providing a thin film shielding effect, a problem occurs in which oxygen or carbon impurities are left behind in the deposition layer due to hydrogen, a typical reactant used in forming metal layers, or ammonia, a typical reactant used in forming metal nitride layers.

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

[0010] The present invention has been made to solve the above-mentioned problems of the prior art, and aims to provide a thin film shielding agent that provides strong and stable physical or chemical adsorption to the surface of a deposition layer on a substrate surface regardless of deposition temperature, thereby significantly improving step coverage and thin film thickness uniformity to form a seamless thin film even when a thin film is formed on a substrate having a complex structure under high temperature conditions, while reducing impurities and improving film quality, and a thin film shielding agent containing the same.

[0011] The present invention aims to provide a method for forming a thin film, which improves the crystallinity and oxidation ratio of the thin film, thereby improving the density, electrical properties, and dielectric properties of the thin film, and a semiconductor substrate manufactured thereby.

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

[0013] In order to achieve the above-mentioned object, the present invention provides a thin film shielding agent used for depositing a metal oxide film or a non-metal oxide film on a substrate, the thin film shielding agent being characterized in that it contains at least one element having an electronegativity between the electronegativity of the metal or non-metal constituting the oxide film and the electronegativity of oxygen, and shields the deposition.

[0014] The metal or nonmetal may be 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.

[0015] The thin film shielding agent may be a compound containing 4 or more elements with an electronegativity in the range of 2.1 to 3.1.

[0016] The thin film shielding agent may be at least one selected from compounds having a structure represented by the following Formula 1:

[0017] [Chemical formula 1] [ka]

[0018]

[0019] (In the above Chemical Formula 1, R 1 are H, OH, and CH 3 , O.C.H. 3 , O.C.H. 2 CH 3 , O.C.H. 2 CH 2 CH 3 or an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkane group having 1 to 5 carbon atoms; and X is [ka] or [ka] and m is an integer of 0 to 4.

[0020] The thin film filter may have a refractive index of 1.4 or more, 1.5 or less, 1.41 to 1.48, or 1.41 to 1.47.

[0021]

[0022] The thin film shielding agent may be one or more selected from the compounds represented by the following formulas 1-1 to 1-9.

[0023] [Chemical formula 1-1~1-9] [ka]

[0024]

[0025] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0026] The thin film deposition layer includes a precursor compound and a thin film shielding agent,

[0027] The thin film shielding agent is the above-mentioned thin film shielding agent, and the precursor compound is a compound represented by the following Chemical Formula 2.

[0028] [Chemical formula 2] [ka]

[0029]

[0030] (In the above formula 2, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd; L 1 , L 2 , L 3 and L 4 are -H, -X, -R, -OR, -NR or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br or I and -R is C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes of C 1 ~C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed into 2 to 6 depending on the oxidation value of the central metal (M).

[0031] As an example, when the central metal is divalent, L 1 and L 2can be attached to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0032]

[0033] The thin film shielding agent provides a shielding region for an oxide film, a nitride film, a metal film, or a selective thin film thereof, and the shielding region may be formed on the entire substrate or a portion of the substrate on which the oxide film, the nitride film, the metal film, or a selective thin film thereof is formed.

[0034] When the total area of ​​the entire or partial substrate (total area of ​​the substrate) is taken as 100%, the shielded area may occupy 10 to 95% of the area, and the unshielded area may occupy the remaining area.

[0035] The thin film can improve the step coverage during the formation of a laminated film of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd.

[0036] 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.

[0037]

[0038] The present invention also provides a method for forming a thin film, comprising the steps of injecting one or more thin film shielding agents selected from compounds having a structure represented by the following formula 1 and a precursor compound into a chamber to form a deposition layer on a substrate loaded thereon.

[0039] [Chemical formula 1] [ka]

[0040]

[0041] (In the above Chemical Formula 1, R 1 are H, OH, and CH 3 , O.C.H. 3 , O.C.H. 2 CH 3 , O.C.H. 2 CH 2 CH 3 or an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkane group having 1 to 5 carbon atoms; and X is [ka] or [ka] and m is an integer of 0 to 4.

[0042] The chamber may be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, or a plasma enhanced chemical vapor deposition (PECVD) chamber.

[0043] The precursor compound and the thin film shielding agent can be delivered into the chamber independently of each other by Vapor Flow Control (VFC), Direct Liquid Introduction (DLI), or Liquid Delivery System (LDS).

[0044] The thin film may be a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0045] The thin film shielding agent may have a deposition rate reduction rate of 20% or more, as represented by the following Equation 1:

[0046] [Formula 1]

[0047] Deposition rate reduction rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0048] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (Initial Deposition Rate) is the deposition rate of the thin film formed without adding any thin film shielding agent. DR f (Final deposition rate) is the deposition rate of the thin film formed by adding an oxide thin film shielding agent when the above process is carried out. Here, the deposition rate (DR) is a value measured by an ellipsometer device under conditions of room temperature and pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.)

[0049] The thin film shielding agent may provide a replacement area for an oxide film, a nitride film, a metal film, or selective films thereof.

[0050] The replacement region may be formed on the entire substrate or a portion of the substrate on which the oxide film, nitride film, metal film, or selective thin film thereof is formed.

[0051] When the total area of ​​the entire substrate or part of the substrate (total area of ​​the substrate) is taken as 100%, the ligand adsorption region may occupy 10 to 95% of the area, and the ligand non-adsorbed region may occupy the remaining area.

[0052] When the total area of ​​the entire substrate or part of the substrate (total area of ​​the substrate) is taken as 100%, the first ligand adsorption region may occupy 10 to 95% of the area, the second ligand adsorption region may occupy 10 to 95% of the remaining area, and the remaining area may be occupied by ligand-unadsorbed regions.

[0053] The thin film may be a laminate film of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd.

[0054] The thin film is used for a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap, and can improve the step coverage during the formation process of these films.

[0055]

[0056] The precursor compound used in the thin film formation method may be a compound represented by the following Chemical Formula 2.

[0057] [Chemical formula 2] [ka]

[0058]

[0059] (In the above formula 2, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd; L 1 , L 2 , L 3and L 4 are -H, -X, -R, -OR, -Cp, -NR or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br or I and -R is C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes of C 1 ~C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed into 2 to 6 depending on the oxidation value of the central metal (M).

[0060]

[0061] In the above formula 2, L 1 , L 2 , L 3 and L 4 are -H, -Cp, or -R, which may be the same or different from each other, where -R is C 1 ~C 10 Alkyl, C 1 ~C 10 or C1-C10 alkanes, which may be linear or cyclic.

[0062] In the above formula 2, L 1 , L 2 , L 3 and L 4 are -H, -Cp, -OR, -NR, or Cp (cyclopentadiene), which may be the same or different from each other, where -R is H, C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes, C 1 ~C 10 alkane, iPr, or TBu.

[0063] In the above formula 2, L 1 , L 2 , L3 and L 4 are -H, -Cp, or -X, which may be the same or different from each other, where -X can be F, Cl, Br, or I.

[0064]

[0065] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0066] i) vaporizing said thin film shielding agent to shield a surface of a substrate loaded into the chamber;

[0067] ii) initially purging the interior of the chamber with a purge gas;

[0068] iii) vaporizing a precursor compound and adsorbing it in an area outside the shielded area;

[0069] iv) second purging the interior of the chamber with a purge gas;

[0070] v) supplying a reaction gas into the chamber;

[0071] vi) a third step of purging the inside of the chamber with a purge gas.

[0072] The precursor compound may be a molecule composed of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may be a precursor having a vapor pressure at 25°C of more than 0.01 mTorr and not more than 100 Torr.

[0073] The chamber may be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, or a plasma enhanced chemical vapor deposition (PECVD) chamber.

[0074] After the thin film shielding agent or precursor compound is vaporized and injected, a plasma post-treatment step may be included.

[0075] The amount of the purge gas introduced into the chamber in each of steps i) and iv) may be 10 to 100,000 times the volume of the introduced thin film shielding agent.

[0076] The reaction gas may be an oxidizing agent, a nitriding agent or a reducing agent, and the reaction gas, the thin film shielding agent and the precursor compound may be delivered into the chamber by a vapor flow control (VFC) method, a direct liquid introduction (DLI) method or a liquid delivery system (LDS) method.

[0077] The thin film may be a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0078] The substrate loaded into the chamber is heated to 100 to 800° C., and the ratio of the thin film shielding agent and the precursor compound fed into the chamber (mg / cycle) may be 1:1 to 1:20.

[0079]

[0080] The present invention also provides a semiconductor substrate comprising a thin film produced by the above-mentioned thin film formation method.

[0081] The thin film may have a multi-layer structure of two or more layers.

[0082]

[0083] The present invention further provides a semiconductor device including the semiconductor substrate described above.

[0084] 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

[0085] According to the present invention, it is possible to provide a thin film shielding agent that effectively shields adsorption to the surface of a substrate, improves the reaction rate, and appropriately reduces the thin film growth rate, thereby improving step coverage even when a thin film is formed under high temperature conditions on a substrate having a complex structure.

[0086] In addition, the process by-products during the formation of the thin film are more effectively reduced, corrosion and deterioration are prevented, and the film quality is modified to improve the crystallinity of the thin film, thereby improving the roughness, dielectric constant, and electrical properties of the thin film.

[0087] Furthermore, the step coverage and density of the thin film can be improved, and further, a thin film forming method using the same and a semiconductor substrate manufactured thereby can be provided. [Brief description of the drawings]

[0088] [Figure 1] FIG. 2 is a diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0089] [Diagram 2] TEM photographs showing the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited without using a thin film shielding agent according to Comparative Example 1, and the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited using a thin film shielding agent.

[0090] [Diagram 3] TEM photographs showing the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited using a thin film shielding agent according to Example 1, and the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited using a thin film shielding agent.

[0091] [Figure 4] TEM photographs showing the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited using a thin film shielding agent according to Example 2, and the film thicknesses deposited at the top (100 nm below the top) and bottom (100 nm above the bottom) of a cross section of an oxide film deposited using a thin film shielding agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0092] The thin film shielding agent described above, the thin film forming method using the same, and the semiconductor substrate produced thereby will be described in detail below.

[0093] In this description, unless otherwise specified, the term "shielding" means not only reducing, preventing or blocking a precursor compound for forming a thin film from being adsorbed onto a substrate, but also reducing, preventing or blocking a process by-product from being adsorbed onto a substrate.

[0094] In this description, unless otherwise specified, the terms "physical adsorption" and "chemical adsorption" are distinguished by whether the adsorption is to an extent that can be removed by purging or whether the adsorption remains even after purging and cannot be removed, and the former is referred to as physical adsorption and the latter as chemical adsorption, respectively.

[0095] The present inventors have found that, in order to form a thin film on the surface of a substrate loaded inside a chamber, a thin film shielding agent capable of effectively shielding the adsorption of a precursor compound to be supplied is used to improve the reaction rate due to the strong and stable physical or chemical adsorption mechanism of the thin film shielding agent on the surface of the deposition layer of the substrate, and that even if a high temperature condition is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is greatly improved by improving the film quality, and in particular, it is possible to deposit the thin film at a thin thickness, and the amount of O, Si, metal, metal oxide, and even the amount of carbon remaining as process by-products, which was difficult to reduce in the past, can be improved. Based on this finding, the present invention has been completed by incorporating it into research on thin film shielding agents.

[0096]

[0097] The thin film may be provided as one or more precursors selected from the group consisting of, for example, Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and may provide an oxide film, a nitride film, or a metal film. In this case, the effects to be achieved in the present invention may be sufficiently obtained.

[0098] Specific examples of the thin film include a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, and an aluminum oxide film.

[0099] The thin film may contain the above-mentioned film compositions alone or as selective areas, but is not limited thereto, and is meant to include SiH and SiOH.

[0100] 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.

[0101]

[0102] The precursor compound used to form the thin film in the present invention is a molecule having Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, or Nd as the central metal atom (M) and one or more ligands described below, and in the case of a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of being replaced with the thin film shielding agent can be maximized.

[0103] As the precursor compound, for example, a compound represented by the following Chemical Formula 2 can be used.

[0104]

[0105] [Chemical formula 2] [ka]

[0106]

[0107] (In the above formula 2, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd; L 1 , L 2 , L 3 and L 4 are -H, -X, -R, -Cp (cyclopentadienyl), -OR, -NR, or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br, or I, and -R is C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes of C 1 ~C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed into 2 to 6 depending on the oxidation value of the central metal (M).

[0108] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0109] In the formula 2, M is hafnium (Hf), silicon (Si), zirconium (Zr) or aluminum (Al), preferably hafnium (Hf) or silicon (Si). In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties, insulating properties and dielectric properties of the thin film are further excellent.

[0110] Said L 1 , L 2 , L 3 and L 4 are -H, -Cp, or -R, which may be the same or different from each other, where -R is C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes of C 1 ~C 10 and may have a linear or cyclic structure.

[0111] In addition, the above-mentioned L 1 , L 2 , L 3 and L 4 are -H, -Cp, -OR, -NR or Cp (cyclopentadiene), which may be the same or different from each other, where -R is H, C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes, C 1 ~C 10 alkane, iPr, or tBu.

[0112] Furthermore, in the above Chemical Formula 1, L 1 , L 2 , L 3 and L 4 are -H, -Cp, or -X, which may be the same or different.

[0113] Specifically, the hafnium precursor compound is, for example, CpHf(NMe 2 ) 3) and Cp(CH 2 ) 3 NM 3 Hf(NMe 2 ) 2 (Methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium and the like can be used.

[0114] Examples of silicon precursor compounds include SiH 4 , SiHCl 3 , SiH 2 Cl 2 , SiCl 4 , Si 2 Cl 6 S 3 Cl 8 , Si 4 Cl 10 , SiH 2 [NH(C 4 H 9 )] 2 , Si 2 (NHC 2 H 5 ) 4 , Si 3 NH 4 (CH 3 ) 3 and SiH 3 [N(CH 3 ) 2 ], SiH 2 [N(CH 3 ) 2 ] 2 , SiH[N(CH 3 ) 2 ] 3 , Si[N(CH 3 ) 2 ] 4 One or more selected from the following can be used.

[0115] Further, examples of aluminum precursor compounds include trimethylaluminum (TMA), tris(dimethylamido)aluminum (TDMAA), aluminum chloride (AlCl 3 ) can be used.

[0116]

[0117] The thin film barrier agent can be used to deposit metal oxide or non-metal oxide films on a substrate.

[0118] The thin film shielding agent contains at least one element having an electronegativity between the electronegativity of the metal or nonmetal constituting the oxide film and the electronegativity of oxygen, and is used to deposit a metal oxide film or a nonmetal oxide film.

[0119] The metal or nonmetal may, for example, shield the surface of a thin 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.

[0120] When the thin film shielding agent is a compound containing 4 or more elements with an electronegativity in the range of 2.1 to 3.1, it has a large effect of reducing process by-products, excellent step coverage, and is more effective in improving the thin film density and electrical properties of the thin film.

[0121] Preferably, the thin film shielding agent may be a compound containing sulfur, phosphorus, or nitrogen. In this case, not only can side reactions be suppressed during thin film formation, the thin film growth rate be controlled, process by-products in the thin film are reduced, corrosion and deterioration are reduced, and the thin film crystallinity is improved, thereby improving film quality. Even when a thin film is formed on a substrate having a complex structure, step coverage and thin film thickness uniformity can be significantly improved.

[0122]

[0123] The thin film shielding agent, preferably a compound containing 4 or more elements with an electronegativity in the range of 2.1 to 3.1, may have a deposition rate reduction rate of 20% or more, specifically 35% or more, as represented by the following mathematical formula 1. In this case, a deposition layer of a uniform thickness due to the difference in the adsorption distribution degree of the shielding agent having the above structure is formed as a shielding region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the formed thin film is significantly reduced, so that even if it is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, it can be deposited into a thin thin film, and the effects of improving O, Si, metal, metal oxide, and even carbon residues that were difficult to reduce in the past, which remain as process by-products, can be provided.

[0124] [Formula 1]

[0125] Deposition rate reduction rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0126] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any thin film shielding agent. DR f (Final Deposition Rate) is the deposition rate of the thin film formed by adding the oxide thin film shielding agent when the above process is carried out. Here, the deposition rate (DR) is the value measured by an ellipsometer device under conditions of room temperature and pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0127] In Equation 1, the thin film growth rate per cycle when the thin film shielding agent is used and when it is not used means the deposition thickness (Å / cycle) of the thin film per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by measuring the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure, and then dividing the measured thickness by the total number of cycles to obtain an average deposition rate.

[0128] In the above formula 1, "when no thin film shielding agent was used" means that only a precursor compound is adsorbed onto a substrate during the thin film deposition process to produce a thin film. A specific example of the thin film formation method is that the step of adsorbing a thin film shielding agent and the step of purging unadsorbed thin film shielding agent are omitted from the thin film formation method.

[0129]

[0130] The thin film shielding agent is characterized by containing linear or cyclic saturated or unsaturated hydrocarbons having two or more types of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) and having 3 to 15 carbon atoms. In this case, when forming a thin film, a shielding region that does not remain in the thin film is formed to form a relatively sparse thin film, and side reactions are suppressed and the thin film growth rate is controlled to reduce process by-products in the thin film, thereby reducing corrosion and deterioration, improving the crystallinity of the thin film, and allowing a stoichiometric oxidation state to be reached during the formation of a metal oxide film. Even when a thin film is formed on a substrate having a complex structure, there are effects of significantly improving step coverage and thin film thickness uniformity.

[0131] The thin film shielding agent contains oxygen (O) or a phenyl group at one or both ends of a central atom, preferably sulfur (S), phosphorus (P), or nitrogen (N), connected to oxygen through a double bond, or contains a compound having a ring structure in which both ends are connected, thereby having a large effect of reducing process by-products and excellent step coverage, as well as an effect of improving thin film density and excellent electrical properties of the thin film.

[0132] The thin film shielding agent may be at least one selected from compounds having a structure represented by the following formula 1, and in this case, when forming a thin film, a substitution region that does not remain in the thin film is formed to form a relatively sparse thin film, and side reactions are suppressed, the thin film growth rate is controlled, and process by-products in the thin film are reduced, corrosion and deterioration are reduced, and the crystallinity of the thin film is improved. Even when a thin film is formed on a substrate having a complex structure, step coverage and thin film thickness uniformity are significantly improved to form a seamless thin film.

[0133] [Chemical formula 1] [ka]

[0134]

[0135] (In the above Chemical Formula 1, R 1 are H, OH, and CH 3 , O.C.H. 3 , O.C.H. 2 CH 3 , O.C.H. 2 CH 2 CH 3 or an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkane group having 1 to 5 carbon atoms; and X is [ka] or [ka] and m is an integer of 0 to 4.

[0136] In the above Chemical Formula 1, R 1 is H or CH 3In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the thin film density is improved, and the electrical properties, insulating properties and dielectric properties of the thin film are further excellent.

[0137] The above m is an integer of 0 to 2, and preferably 0 or 1.

[0138]

[0139] The thin film shielding agent can be, for example, a compound having a refractive index in the range of 1.4 or more and 1.5 or less, 1.41 to 1.48, or 1.41 to 1.47.

[0140] In such a case, the thin film shielding agent having the above-mentioned structure on the substrate can adequately shield the adsorption of the precursor compound on the substrate by a strong and stable physical or chemical adsorption mechanism of the thin film shielding agent on the surface of the deposition layer of the substrate, thereby improving the reaction rate, and even when a thin film is formed on a substrate having a complex structure under high temperature conditions, the step coverage and the thickness uniformity of the thin film are significantly improved, and not only the thin film precursor but also the process by-products are prevented from being adsorbed, thereby effectively protecting the surface of the substrate and effectively removing the process by-products.

[0141]

[0142] When the shielding agent is, for example, a compound represented by Chemical Formula 1, the compound may have a refractive index within the range of 1.4 or more and 1.5 or less, 1.41 to 1.48, or 1.41 to 1.47.

[0143] In such a case, a uniformly thick deposition layer is formed on the substrate due to the difference in the adsorption distribution of the shielding agent having the above-mentioned structure, and a shielding region is formed that does not remain in the thin film, thereby reducing the deposition rate of the thin film and appropriately lowering the thin film growth rate. This has the advantage that even when a thin film is formed on a substrate having a complex structure under high temperature conditions, the step coverage and the uniformity of the thin film thickness are greatly improved to form a seamless thin film, and not only the thin film precursor but also the process by-products are prevented from being adsorbed, thereby effectively protecting the surface of the substrate and effectively removing the process by-products.

[0144] In particular, a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the thin film is applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide an effect of improving the amount of O, Si, metal, metal oxide, and even carbon residues that are left as process by-products and that were previously difficult to reduce.

[0145]

[0146] The thin film shielding agent may include at least one selected from the compounds represented by the following formulas 1-1 to 1-9. In this case, it has a great effect of controlling the growth rate of the thin film by providing a thin film shielding region, and has a great effect of removing process by-products, as well as an excellent effect of improving step coverage and film quality.

[0147] [Chemical formula 1-1~1-9] [ka]

[0148]

[0149] The thin film forming composition containing the thin film shielding agent may comprise a precursor compound constituting a thin film deposition layer and a thin film shielding agent.

[0150] The precursor compound may be a compound represented by the following formula 2:

[0151] [Chemical formula 2] [ka]

[0152]

[0153] (In the above formula 2, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd; L 1 , L 2 , L 3 and L 4 are -H, -X, -R, -Cp, -OR, -NR, or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br, or I, and -R is C 1 ~C 10 Alkyl, C 1 ~C 10 Alkenes of C 1 ~C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed into 2 to 6 depending on the oxidation value of the central metal (M).

[0154] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0155]

[0156] The thin film shielding agent provides a shielding region for an oxide film, a nitride film, a metal film, or a selective thin film thereof, and the shielding region is formed on the entire substrate or a portion of the substrate on which the oxide film, the nitride film, the metal film, or a selective thin film thereof is formed.

[0157] The shielding region for the thin film is characterized in that it does not remain on the thin film.

[0158] In this case, unless otherwise specified, "not remaining" refers to the presence of C element at 0.1 atomic % (atom %), Si element at less than 0.1 atomic % (atom %), N element at less than 0.1 atomic % (atom %), and halogen element at less than 0.1 atomic % (atom %) when the components are analyzed by X-ray photoelectron spectroscopy (XPS). More preferably, in a measurement method using secondary ion mass spectrometry (SIMS) in which measurements are made while digging into the substrate in the depth direction, or a measurement method using X-ray photoelectron spectroscopy (XPS), when considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using an activator under the same deposition conditions, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0159] As a specific example, when the total area of ​​the entire substrate or part of the substrate (total area of ​​the substrate) is taken as 100%, the shielded area may occupy 10 to 95% of the area, and the unshielded area may occupy the remaining area.

[0160] For example, the thin film may contain 100 ppm or less of halogen compounds. For reference, if an excessive amount of halogen remains, when a nitriding agent is used under the temperature conditions of 200 to 300° C., which are the experimental conditions described below, NH 4 This is undesirable because it generates impurities with high boiling points, such as Cl, which remain in the thin film.

[0161] The thin film can be used as an etching stop layer, an electrode layer, a dielectric layer, a gate insulating layer, a block oxide layer, or a charge trap, and can be used in semiconductor devices by improving step coverage during the formation of these layers.

[0162] The thin film shielding agent can be preferably a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, if a compound with a purity of less than 99% is used, impurities may remain in the thin film or cause side reactions with the precursor or reactant, so it is preferable to use a substance with a purity of 99% or more as much as possible.

[0163]

[0164] The thin film shielding agent is preferably used in an atomic layer deposition (ALD) process, and in this case, it has the advantages of effectively protecting the surface of the substrate by being used as a thin film shielding agent while not interfering with the adsorption of the precursor compound, and effectively removing process by-products.

[0165] The thin film shielding agent preferably has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 and the vapor pressure (20° C.) may be 0.1 to 300 mmHg or 1 to 300 mmHg.

[0166] More preferably, the thin film shielding agent has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.3g / cm 3 and the vapor pressure (20° C.) can be 1 to 260 mmHg.

[0167]

[0168] In particular, a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the thin film is applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide an effect of improving the amount of O, Si, metal, metal oxide, and even carbon residues that are left as process by-products and that were previously difficult to reduce.

[0169]

[0170] The thin film formation method of the present invention is characterized by including a step of forming a deposition layer on a substrate loaded with the above-mentioned thin film shielding agent by injecting the thin film shielding agent into a chamber. In this case, by performing a physical or chemical reaction on the surface of the substrate, the reaction rate is improved and the thin film growth rate is appropriately reduced, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed under high temperature conditions on a substrate having a complex structure.

[0171]

[0172] In the step of shielding the thin film shielding agent on the surface of the substrate, the feeding time (seconds (sec)) of the thin film shielding agent on the surface of the substrate is preferably 0.01 to 5 seconds per cycle, more preferably 0.02 to 3 seconds, even more preferably 0.04 to 2 seconds, and even more preferably 0.05 to 1 second. Within this range, there are advantages such as a low thin film growth rate, excellent step coverage, and excellent cost-effectiveness.

[0173] In this description, the feeding time of the thin film shielding agent is based on a flow rate of 0.1 to 500 mg / cycle in a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle in a chamber volume of 18 L.

[0174]

[0175] In a preferred embodiment, the thin film forming method may include the steps of i) vaporizing the thin film shielding agent to shield the surface of the substrate loaded into the chamber, ii) purging the inside of the chamber with a purge gas, iii) vaporizing a precursor compound to adsorb it to an area outside the shielding area, iv) purging the inside of the chamber with a purge gas, v) supplying a reaction gas into the chamber, and vi) purging the inside of the chamber with a purge gas. At this time, the steps i) to vi) are regarded as a unit cycle, and the cycle can be repeated until a thin film of a desired thickness is obtained (see FIG. 1 below). In this way, when the thin film shielding agent of the present invention is added before the precursor compound in one cycle to be adsorbed on the substrate, and the thin film shielding agent is added after the precursor compound to improve the film quality, even if the deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, and the resistivity of the thin film can be reduced by effectively removing the process by-products generated, and the step coverage is significantly improved.

[0176] As a preferred example, the thin film forming method of the present invention can be adsorbed on the substrate by adding the thin film shielding agent of the present invention before the precursor compound in one cycle. In this case, even if the thin film is deposited at a high temperature, the thin film growth rate can be appropriately reduced, so that the process by-products can be significantly reduced, the step coverage can be significantly improved, the crystallinity of the thin film can be increased, and the resistivity of the thin film can be reduced. Even if the thin film is applied to a semiconductor device with a large aspect ratio, the thickness uniformity of the thin film can be significantly improved, ensuring the reliability of the semiconductor device.

[0177]

[0178] In the thin film forming method, when the thin film shielding agent is deposited before or after the deposition of the precursor compound, the unit cycle can be repeated 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, the effect to be achieved in the present invention can be sufficiently obtained while obtaining the target thin film thickness.

[0179]

[0180] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

[0181] In the present invention, the thin film shielding agent or precursor compound may be vaporized and injected, followed by a plasma post-treatment step, in which case the thin film growth rate can be improved while reducing process by-products.

[0182]

[0183] When the thin film shielding agent is injected on the substrate in a cross injection manner and the precursor compound is adsorbed between them, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed thin film shielding agent is not particularly limited as long as it is an amount sufficient to remove the unadsorbed thin film shielding agent, but may be 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed thin film shielding agent is sufficiently removed to form a thin film uniformly and prevent deterioration of film quality. Here, the amounts of the purge gas and the thin film shielding agent introduced are based on one cycle, and the volume of the thin film shielding agent means the volume of vaporized thin film shielding agent vapor.

[0184] As a specific example, in the step of injecting the thin film shielding agent (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and purging unadsorbed thin film shielding agent, when a purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec, the amount of purge gas injected is 602 times the amount of thin film shielding agent injected.

[0185]

[0186] In addition, in the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the chamber is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor compound, but as an example, it may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the precursor compound introduced into the chamber, and within this range, the unadsorbed precursor compound can be sufficiently removed to form a uniform thin film and prevent deterioration of the film quality. Here, the amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound means the volume of the vaporized precursor compound vapor.

[0187]

[0188] Furthermore, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the chamber may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, 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 the purge gas and reaction gas introduced are each based on one cycle.

[0189]

[0190] The thin film shielding agent and the precursor compound can be preferably delivered into the chamber by the VFC method, the DLI method or the LDS method, and more preferably, are delivered into the chamber by the LDS method.

[0191] The substrate loaded in the chamber may be heated to, for example, 50 to 400°C, specifically, 50 to 400°C, and the thin film shielding agent or precursor compound may be injected onto the substrate in an unheated or heated state, and the heating conditions may be adjusted during the deposition process after being injected unheated depending on deposition efficiency. For example, the thin film shielding agent or precursor compound may be injected onto the substrate at 50 to 400°C for 1 to 20 seconds.

[0192]

[0193] The ratio of the amount (mg / cycle) of the thin film shielding agent to the precursor compound fed into the chamber may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and the effect of reducing process by-products are large.

[0194]

[0195] In the present invention, the precursor compound may be mixed with a non-polar solvent and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0196] The non-polar solvent may be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, the non-polar solvent has the advantage of improving step coverage even when the deposition temperature is increased during the formation of a thin film, while containing an organic solvent having low reactivity and solubility and easy moisture management.

[0197] In a more preferred example, the non-polar solvent is 1 ~C 10 Alkane or C 3 ~C 10 and preferably C 3 ~C10 In this case, the reactivity and solubility are low, and water management is easy.

[0198] In this description, C 1 , C 3 etc. mean the number of carbon atoms.

[0199] The cycloalkane is preferably 3 ~C 10 Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, and therefore is suitable for the vapor deposition process, but is not limited thereto.

[0200] The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantages of low reactivity with the precursor compound and easy moisture control.

[0201] In this description, the solubility is not particularly limited to the measurement methods and standards commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by high performance liquid chromatography (HPLC).

[0202] The non-polar solvent may preferably comprise 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0203] If the content of the non-polar solvent exceeds the upper limit, impurities are induced, and the value of impurities in the resistivity and thin film increases. If the content of the organic solvent is less than the lower limit, the effect of improving step coverage and the effect of reducing impurities such as chlorine (Cl) ions by adding the solvent are not obtained.

[0204]

[0205] In the thin film forming method, when the thin film shielding agent is used, the deposition rate reduction rate represented by the following formula 1 can be 30% or more, specifically 35% or more. In this case, a deposition layer of a uniform thickness due to the difference in the adsorption distribution degree of the activator having the above structure is formed as a replacement region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the formed thin film is significantly reduced, so that even if it is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, it is possible to provide an effect that it is possible to deposit a thin thin film, and O, Si, metal, metal oxide, and even carbon residues that were difficult to reduce as process by-products are improved.

[0206] [Formula 1]

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

[0208] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any thin film shielding agent. DR f (Final Deposition Rate) is the deposition rate of the thin film formed by adding an oxide thin film shielding agent when the above process is carried out. Here, the deposition rate (DR) is the value measured by an ellipsometer device under conditions of room temperature and pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0209]

[0210] In the thin film formation method, the strength (c / s) of residual halogen in the thin film based on a thin film thickness of 100 Å, measured based on SIMS, can be preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less, 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 a range, the effect of preventing corrosion and deterioration is outstanding.

[0211] In this description, the purge rate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeters per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition is performed as or approximately as an atomic mono-layer, which is advantageous in terms of film quality.

[0212]

[0213] The ALD (atomic layer deposition) process is very advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and has advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin film growth mechanism.

[0214] The thin film formation method can be carried out at a deposition temperature in the range of, for example, 50 to 800°C, preferably at a deposition temperature in the range of 100 to 700°C, more preferably at a deposition temperature in the range of 200 to 650°C, even more preferably at a deposition temperature in the range of 220 to 400°C, and even more preferably at a deposition temperature in the range of 220 to 300°C. Within this range, there is an effect of growing a thin film with excellent film quality while realizing the ALD process characteristics.

[0215] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, there is an effect that a thin film with a uniform thickness can be obtained.

[0216] In this description, deposition temperature and deposition pressure may be measured as the temperature and pressure established within a deposition chamber, or may be measured as the temperature and pressure applied to a substrate within the deposition chamber.

[0217] The thin film formation method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the thin film shielding agent into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the thin film shielding agent into the chamber.

[0218] 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 thin film shielding agent, a first conveying means for conveying the vaporized thin film shielding agent into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second conveying means for conveying the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and the conveying means are not particularly limited as long as they are vaporizers and conveying means commonly used in the technical field to which the present invention pertains.

[0219] The first vaporizer for vaporizing the thin film shielding agent may be divided into at least two types, such as a vaporizer for vaporizing the thin film shielding agent and a vaporizer for vaporizing the thin film shielding agent, as necessary.

[0220] As a specific example, the method for forming the thin film will be described below. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of depositing atomic layers.

[0221] The substrate may be a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0222] The substrate may further have a conductive or insulating layer formed thereon.

[0223] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned thin film shielding agent and a precursor compound or a mixture thereof with a non-polar solvent are prepared.

[0224] Then, the prepared thin film barrier agent (e.g., thin film barrier agent) is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto a substrate, and then purged to remove unadsorbed thin film barrier agent.

[0225] Next, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (a composition for forming a thin film) is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber where it is adsorbed onto a substrate and shielded by a thin film shielding agent that was previously injected, and any unadsorbed precursor compound or a mixture of the precursor compound and a non-polar solvent is purged.

[0226] Then, the prepared thin film barrier agent is injected into a vaporizer, converted into a vapor phase, and delivered to a deposition chamber for adsorption, and the unadsorbed thin film barrier agent is purged.

[0227] In this description, the method of delivering the thin film shielding agent and the precursor compound (thin film forming composition) to the deposition chamber may be, for example, a method of delivering a volatilized gas using a mass flow controller (MFC) (Vapor Flow Control: VFC), or a method of delivering a liquid using a liquid mass flow controller (LMFC) (Liquid Delivery System: LDS), and preferably the LDS method is used.

[0228] At this time, the carrier gas or dilution gas for moving the thin film shielding agent and the precursor compound onto the substrate is argon (Ar), nitrogen (N 2 One or a mixture of two or more gases selected from the group consisting of, but not limited to, argon (Ar) and helium (He) can be used.

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

[0230]

[0231] Then, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably include a nitriding agent. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0232] Preferably, the nitriding agent is nitrogen gas (N 2 ), hydrazine gas (N 2 H 4 ), or a mixture of nitrogen and hydrogen gas.

[0233] The remaining unreacted reactant gas is then purged with an inert gas, which removes not only the excess reactant gas but also any by-products that are produced.

[0234] As described above, the thin film forming method, for example, has a unit cycle including the steps of supplying a thin film shielding agent onto a substrate, purging unadsorbed thin film shielding agent, adsorbing a precursor compound / thin film forming composition onto a substrate, purging unadsorbed precursor compound, supplying a reactive gas, and purging residual reactive gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0235] The unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film properties can be effectively exhibited.

[0236]

[0237] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described above. In such a case, the thin film has excellent step coverage and thickness uniformity, and has excellent density and electrical properties.

[0238]

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

[0240] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 25 nm, and even more preferably 5 to 20 nm. Within this range, the thin film has excellent thin film properties.

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

[0242] The thin film may have a halogen content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm. Within this range, the thin film has excellent thin film properties while having a reduced thin film growth rate. Here, the halogen remaining in the thin film is, for example, Cl. 2 , Cl, or Cl - The lower the amount of residual halogen in the thin film, the better the film quality, which is preferable.

[0243] As an example, the thin film has a step coverage of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even if the thin film has a complex structure, it can be easily deposited on a substrate, and has the advantage that it can be applied to next-generation semiconductor devices.

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

[0245]

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

[0247] The underlayer film may be, for example, Si, SiO 2 , MgO, Al 2 O 3 , CaO, ZrSiO 4 , ZrO 2 , HfSiO 4 , Y 2 O 3 , HfO 2 , LaLuO 2 , Si 3 N 4 , SrO, La 2 O 3 , Ta 2 O 5 , BaO, TiO 2 The composition may comprise one or more selected from the group consisting of:

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

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

[0250]

[0251] Below, preferred embodiments and drawings are presented to deepen understanding of the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the technical spirit thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0252]

[0253] [Example]

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

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

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

[0257] Specifically, as the thin film shielding agent, a compound represented by Chemical Formula 1-4 and a compound represented by the following Chemical Formula 3-1 were prepared.

[0258] [Chemical formula 1-4] [ka]

[0259]

[0260] [Chemical formula 3-1] [ka]

[0261]

[0262] The precursor is CpHf(NMe 2 ) 3 ) tris(dimethylamido)cyclopentadienylhafnium (represented as CpHf in the table below) and trimethylaluminum (represented as TMA in the table below) were prepared.

[0263] While flowing argon into the chamber at 5000 ml / min, the pressure inside the chamber was adjusted to 1.5 Torr using a vacuum pump to form a thin inert atmosphere.

[0264] The thin film shielding agent prepared as shown in Table 1 below was placed in a canister, and the partial pressure and temperature were adjusted to the injection amount (mg / cycle). The canister was then loaded into a deposition chamber with a substrate loaded therein for 1 second to coat the substrate, and the chamber was purged for 10 seconds.

[0265] The precursor compounds were then loaded into a canister and introduced into the deposition chamber using a Vapor Flow Controller (VFC) as shown in Table 1, and the chamber was purged for 10 seconds.

[0266] Then, O was used as a reactive gas. 2 Inside O 3 The concentration is 200g / m 3 The mixture was placed in a deposition chamber so that the temperature became equal to or greater than 100° C., as shown in Table 1, and the chamber was purged for 10 seconds. At this time, the substrate on which the thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0267] This process was repeated 100 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0268] For each of the obtained thin films of Examples 1 to 2 and Comparative Examples 1 to 3, the deposition rate reduction rate (D / R reduction rate), secondary ion mass spectrometry (SIMS) C impurities, and step coverage were measured by the following method, and the results are shown in Table 1 below.

[0269] * Deposition rate reduction rate (D / R (dep.rate) reduction rate): This refers to the ratio of the deposition rate reduction after the introduction of the shielding agent compared to the D / R before the introduction of the shielding agent, and was calculated as a percentage using the measured Å / cycle values.

[0270] Specifically, the film thickness of the thin film was measured using an ellipsometer, which is a device capable of measuring optical properties such as the film thickness and refractive index of the thin film using the polarization properties of light, and divided by the number of cycles to calculate the film thickness deposited per cycle, and the reduction rate of the thin film growth rate was calculated. Specifically, it was calculated using the following Equation 1.

[0271] [Formula 1]

[0272] Deposition rate reduction rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0273] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any thin film shielding agent. DR f (Final Deposition Rate) is the deposition rate of the thin film formed by adding the oxide thin film shielding agent when the above process is carried out. Here, the deposition rate (DR) is the value measured by using an ellipsometer device under conditions of room temperature and normal pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0274]

[0275] *The non-uniformity was calculated by selecting the maximum and minimum film thicknesses among those measured by the ellipsometer and using the following Equation 2, and the results are shown in Table 1. Specifically, the film thickness was measured at four points on the north, south, east and west edges of a 300 mm wafer and at one point in the center.

[0276] [Formula 2]

[0277] Nonuniformity % = [{(maximum thickness - minimum thickness) / 2} x average thickness] x 100

[0278]

[0279] * SIMS (Secondary-ion mass spectrometry) C impurity: While ion sputtering was used to dig into the thin film in the axial direction, the C impurity content (counts) in the surface layer of the substrate was checked considering the sputtering time of 50 seconds, which is the least contaminated, and the C impurity value in the SIMS graph was confirmed and shown in Table 1 below.

[0280] *Step coverage (%): The thin films deposited on a substrate with a complex structure having an aspect ratio of 22:1 according to Examples 1-2 and Comparative Examples 1-3 were horizontally cut at a position 100 nm from the top to the bottom (left image) and at a position 100 nm from the bottom to the top (right image). The step coverage was measured using a transmission electron microscope (TEM) and calculated according to the following formula 3.

[0281] [Formula 3]

[0282] Step coverage % = (film thickness deposited on the lower inner wall / film thickness deposited on the upper inner wall) x 100

[0283]

[0284] [Table 1]

[0285] In the table, CpHf is an abbreviation of Tris(dimethyl amido)cyclopentadienyl hafnium, and TMA is an abbreviation of Trimethylaluminum. As shown in Table 1, it was confirmed that Examples 1 and 2 using the thin film shielding agent according to the present invention not only have a significantly improved deposition rate reduction rate compared to Comparative Examples 1 and 3 not using the thin film shielding agent, but also have excellent impurity reduction properties.

[0286] Specifically, the non-uniformity of Example 1, 1.93%, was not only much lower than the non-uniformity of Comparative Example 1, 8.33%, but also the GPC reduction effect was 45%, which was a significant improvement over the 20% level of Comparative Example 1.

[0287] Specifically, as is clear from Figures 2 to 4, it was confirmed that the thin films prepared in Examples 1 and 2 using the thin film shielding agent according to the present invention provided an increased film thickness at both the top and bottom compared to Comparative Example 1 in which no thin film shielding agent was used.

[0288] In addition, in Examples 1 and 2 using the thin film shielding agent according to the present invention, it was confirmed that not only was the deposition rate reduction rate improved significantly compared to Comparative Example 2 using other types of thin film shielding agents, such as dimethyl sulfoxide, which are not considered to be suitable, but also that the impurity reduction characteristics were excellent.

[0289]

[0290] *Specifically, the step coverage in Example 1, in which the thin film shielding agent of the present invention was used, was 45%, which was more than twice as good as the step coverage of 20% in Comparative Example 2, in which dimethyl sulfoxide was used.

Claims

1. 1. A thin film shielding agent for use in depositing a metal oxide or non-metal oxide film on a substrate, comprising: A thin film shielding agent, comprising at least one element having an electronegativity between the electronegativity of the metal or nonmetal constituting the oxide film and the electronegativity of oxygen, and capable of shielding the deposition.

2. The thin film shielding agent according to claim 1, characterized in that the metal or nonmetal shields the surface of a thin 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.

3. The thin film shielding agent according to claim 1, characterized in that the thin film shielding agent is a compound containing 4 or more elements having an electronegativity in the range of 2.1 to 3.

1.

4. The thin film shielding agent according to claim 1, wherein the thin film shielding agent is a compound having a structure represented by the following Chemical Formula 1: [Chemical formula 1] 【Chemistry 1】 (In the above Chemical Formula 1, R １ is H, OH, CH ３ , O.C.H. ３ , O.C.H. ２ CH ３ , O.C.H. ２ CH ２ CH ３ or an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkane group having 1 to 5 carbon atoms; 【Chemistry 2】 or 【Chemistry 3】 and m is an integer from 0 to 4.

5. The thin film shielding agent according to claim 1, wherein the thin film shielding agent is at least one selected from the compounds represented by the following formulas 1-1 to 1-9. [Chemical formulas 1-1 to 1-9] 【Chemistry 4】

6. The thin film deposition layer includes a precursor compound and a thin film shielding agent, The thin film shielding agent is a thin film shielding agent according to any one of claims 1 to 5, The precursor compound is a compound represented by the following chemical formula 2: [Chemical formula 2] 【Chemistry 5】 (In the above formula 2, M is at least one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd; L １ , L ２ , L ３ and L ４ are -H, -X, -R, -OR, -NR, or Cp (cyclopentadiene), which may be the same or different from each other, where -X is F, Cl, Br, or I, and -R is C １ ~C １０ Alkyl, C １ ~C １０ or C １ ~C １０ which may be linear or cyclic, １ , L ２ , L ３ and L ４ can be formed from 2 to 6 depending on the oxidation value of the central metal (M).

7. 7. The thin film forming composition according to claim 6, wherein the thin film shielding agent provides a shielding region for an oxide film, a nitride film, a metal film, or a selective thin film thereof, and the shielding region is formed on the entire substrate or a portion of the substrate on which the oxide film, the nitride film, the metal film, or a selective thin film thereof is formed.

8. The thin film forming composition according to claim 6, wherein, when the total area of ​​the entire substrate or a portion of the substrate (total area of ​​the substrate) is taken as 100%, the shielded region occupies 10 to 95% of the area, and the unshielded region occupies the remaining area.

9. The thin film forming composition according to claim 6, characterized in that the thin film improves step coverage during the formation of a laminate film of one or more elements selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce and Nd.

10. A method for forming a thin film, comprising the steps of injecting at least one thin film shielding agent selected from compounds having a structure represented by the following formula 1 and a precursor compound into a chamber to form a deposition layer on a substrate loaded thereon. [Chemical formula 1] 【Chemistry 6】 (In the above Chemical Formula 1, R １ is H, OH, CH ３ , O.C.H. ３ , O.C.H. ２ CH ３ , O.C.H. ２ CH ２ CH ３ or an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, or an alkane group having 1 to 5 carbon atoms; 【Chemistry 7】 or 【Chemistry 8】 and m is an integer from 0 to 4.

11. 11. The method of claim 10, wherein the precursor compound and the thin film shielding agent are delivered into the chamber independently of each other by a vapor flow control (VFC), a direct liquid introduction (DLI), or a liquid delivery system (LDS), and the thin film is a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

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

13. 13. The semiconductor substrate according to claim 12, wherein the thin film has a multi-layer structure of two or more layers.

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

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