Vacuum-based thin film modifier, thin film modifier composition containing the same, thin film forming method using the same, semiconductor substrate and semiconductor device manufactured by the same

Abstract

The present invention relates to a vacuum-based thin film modifier, a thin film modifier composition containing the same, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. By providing a compound having a specific structure as a vacuum-based thin film modifier, the growth rate of a deposited film in a vacuum-based thin film process can be appropriately reduced, and 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, etching efficiency can be improved, and impurity contamination such as carbon can be significantly reduced.

Description

[Technical field]

[0001] The present invention relates to a vacuum-based thin film modifier, a thin film modifier composition containing the same, a thin film forming method using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. More specifically, the present invention relates to a vacuum-based thin film modifier, which provides a compound having a predetermined structure as a vacuum-based thin film modifier, thereby appropriately reducing the growth rate of a deposited film in a vacuum-based thin film process, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, improving etching film efficiency, and significantly reducing impurity contamination such as carbon, a thin film modifier composition containing the same, a thin film forming method using the same, and a semiconductor substrate manufactured thereby. [Background technology]

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

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

[0004] As a result, step coverage, which limits the thickness ratio of the deposition layer formed on the top and bottom of the microstructure in the depth direction, remains at a level of 90%, making it increasingly difficult for the electrical characteristics of devices to be expressed, and this is becoming increasingly important. 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] The semiconductor thin film is made of a nitride film, a thin film, a metal film, etc. Examples of the nitride film include silicon nitride (SiN), titanium nitride (TiN), tantalum nitride (TaN), etc., examples of the thin film include silicon oxide (SiO2), hafnium oxide (HfO2), zirconium oxide (ZrO2), etc., and examples of the metal film include molybdenum film (Mo), tungsten (W), etc.

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

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

[0008] When the deposition temperature is increased in order to achieve 100% step coverage, difficulties arise in terms of step coverage. First, in a deposition process that involves two types of material, a precursor and a reactant, an increase in deposition temperature not only leads to a steep increase in the growth rate of the thin film (GPC: Growth Per Cycle), but also, even if an ALD process is performed at 300°C in order to mitigate the increase in GPC caused by an increase in deposition temperature, the deposition temperature increases during the process, making it difficult to say that this is a solution.

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

[0010] However, the higher the deposition temperature, the more difficult it becomes to ensure the step coverage. First, in a deposition process that involves two types of materials, a precursor and a reactant, an increase in deposition temperature may lead to a steep increase in the thin film growth rate (GPC: Growth Per Cycle). In addition, even if a known shielding agent is used to mitigate the increase in GPC caused by an increase in deposition temperature, it has been confirmed that the GPC increases by about 10% at 300°C. In other words, when deposition is performed at 360°C or higher, it becomes difficult to expect the GPC reduction effect provided by conventionally known shielding agents.

[0011] Therefore, there is a demand for a thin film formation method that can effectively form thin films with complex structures even at high temperatures, with a small amount of residual impurities, and significantly improves step coverage and thin film thickness uniformity, as well as semiconductor substrates and the like manufactured thereby. Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above-mentioned problems of the prior art, and aims to provide a vacuum-based thin film modifier that appropriately reduces the thin film growth rate during a vacuum-based thin film process by providing a compound having a specific structure, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurity contamination, a thin film formation method using the same, and a semiconductor substrate manufactured thereby.

[0013] The present invention aims to improve the density and dielectric properties of thin films by improving the crystallinity and oxidation fraction of the thin films.

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

[0015] In order to achieve the above object, the present invention provides a vacuum-based thin film modifier comprising an aromatic compound having a hydrocarbon group and a halogen group, which is characterized by controlling the growth or film quality of a vacuum-based thin film formed from a precursor compound.

[0016] The vacuum-based thin film can be a vacuum-based deposited film or a vacuum-based etched film.

[0017] The aromatic compound having a hydrocarbon group and a halogen group may include a compound represented by the following Chemical Formula 1.

[0018] chemical formula 1

[0019] [ka]

[0020] (In the above Chemical Formula 1, R', R" and X are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, and each contains at least one halogen group.)

[0021] In the above Chemical Formula 1, R', R'', and X may be hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively.

[0022] The aromatic compound having a hydrocarbon group and a halogen group may have a refractive index of 1.50 to 1.60, 1.50 to 1.58, or 1.51 to 1.57.

[0023] When the thin film is a vapor-deposited film, the vacuum-based thin film modifier may include a compound represented by the following chemical formulas 1-1 to 1-2.

[0024] Chemical formula 1-1~1-2

[0025] [ka]

[0026] When the thin film is an etching film, the vacuum-based thin film modifier may include compounds represented by the following chemical formulas 1 to 3.

[0027] Chemical formula 1-3

[0028] [ka]

[0029] The vacuum-based thin film modifier can control the reactive aspects of thin films formed from silane-based precursor compounds.

[0030]

[0031] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0032] A vacuum-based thin film modifying composition is provided, comprising the vacuum-based thin film modifying agent and an organic solvent having a dielectric constant of 15 or less.

[0033]

[0034] The organic solvent having a dielectric constant of 15 or less may be a hydrocarbon solvent or a heterocycle-containing solvent.

[0035] The organic solvent having a dielectric constant of 15 or less is octane, dimethylethylamine or tetrahydrofuran.

[0036]

[0037] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0038] Treating a surface of a substrate loaded into the chamber with the vacuum-based thin film modifier or the vacuum-based thin film modifier composition;

[0039] and sequentially injecting a precursor compound and a reactive gas into a chamber to form a vacuum-based deposited thin film on the substrate at 20 to 800°C and a vacuum of less than 760 torr, wherein the reactive gas is an oxidizing agent or a reducing agent.

[0040] 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.

[0041] The vacuum-based thin film modifier, vacuum-based thin film modifier composition, and 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.

[0042] At this time, the heating temperature of the deposition transfer line (hereinafter, referred to as the "injection line") may be within the range of 25 to 200°C for the substrate.

[0043] The thin film may be an oxide film or a nitride film.

[0044] The reactive gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0045] The thin film may be a thin film having one or more layers of one or more metals selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd laminated thereon.

[0046] 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 blocking thin film, or a charge trap.

[0047]

[0048] The present invention also provides a method for producing a semiconductor device comprising the steps of:

[0049] treating a surface of a substrate loaded into the chamber with said vacuum-based thin film modifier or said vacuum-based thin film modifier composition;

[0050] injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate; The etching material is at least one selected from the group consisting of Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0051] The chamber can be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0052] The vacuum-based thin film modifier, vacuum-based thin film modifier composition and precursor compound can be delivered into the chamber by a VFC method, a DLI method or an LDS method.

[0053] The etching agent can be mixed with Ar, H2, or O2.

[0054]

[0055] The thin film modification method includes:

[0056] i) vaporizing said vacuum-based thin film modifier or thin film modification composition to form a modified region on a surface of a substrate loaded in the chamber;

[0057] ii) a step of primarily purging the inside of the chamber with a purge gas.

[0058]

[0059] The thin film forming method includes:

[0060] i) vaporizing said vacuum-based thin film modifier or thin film modification composition to form a modified region on a surface of a substrate loaded in the chamber;

[0061] ii) initially purging the interior of the chamber with a purge gas;

[0062] iii) vaporizing a precursor compound and adsorbing it in an area outside the modified area;

[0063] iv) second purging the interior of the chamber with a purge gas;

[0064] v) supplying a reaction gas into the chamber;

[0065] vi) a third step of purging the inside of the chamber with a purge gas.

[0066]

[0067] The vacuum-based thin film modifier or thin film modifier composition may be applied to a substrate loaded in a chamber under a temperature condition of 20 to 800°C.

[0068] 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.

[0069] The thin film modifier, thin film modifier composition, or precursor compound may be vaporized and injected, followed by a plasma post-treatment step.

[0070] In the steps i) and iv), the amount of purge gas introduced into the chamber may be 10 to 100,000 times the volume of the introduced thin film modifier, thin film modifier composition, or precursor compound.

[0071] The reactive gas may be an oxidant or a reductant, and the reactive gas, vacuum-based thin film modifier, thin film modifier composition and precursor compound may be delivered into the chamber by a VFC method, a DLI method or an LDS method.

[0072] The substrate loaded into the chamber is heated to 100 to 800° C., and the ratio of the vacuum-based thin film modifier or thin film modifier composition to the precursor compound in the chamber (mg / cycle) may be 1:1 to 1:20.

[0073]

[0074] The present invention also provides a semiconductor substrate comprising a thin film produced by the above-mentioned thin film formation method.

[0075] The thin film may have a multi-layer structure of two or more layers.

[0076] The present invention further provides a semiconductor device including the semiconductor substrate described above.

[0077] 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

[0078] According to the present invention, it is possible to provide a vacuum-based thin film modifier or thin film modifier composition that can significantly improve step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure by appropriately reducing the thin film growth rate during a vacuum-based thin film process, and can significantly reduce impurity contamination such as carbon.

[0079] In addition, the process by-products during the formation of the thin film are more effectively reduced, corrosion and deterioration are prevented, and the film quality is modified to improve the crystallinity of the thin film, thereby improving the electrical characteristics of the thin film.

[0080] Furthermore, when forming a thin film, the process by-products are reduced, the reaction rate is lowered, and the thin film growth rate is appropriately reduced, so that even when a thin film is formed on a substrate having a complex structure, the step coverage and thin film density can be improved, and further, a thin film formation method using this and a semiconductor substrate manufactured thereby can be provided. [Brief description of the drawings]

[0081] [Figure 1] 1 is a diagram showing the presence or absence of carbon residue in a 10 nm-thick SiN thin film prepared using the thin film modifying composition according to the present invention, which was subjected to XPS depth analysis.

[0082] [Diagram 2] 1 is a graph showing 1H-NMR measurements to confirm the reactivity during synthesis and deposition of a thin film modifying composition, in which octane is mixed with 1-chloroethylbenzene. [Diagram 3] 1 is a graph showing the results of 1H-NMR measurements to confirm the reactivity of the thin film modifying composition during synthesis and deposition, in which dimethylethylamine (DMEA) is mixed with 1-chloroethylbenzene. [Figure 4] 1 is a graph showing 1H-NMR measurements to confirm the reactivity during synthesis and deposition of a thin film modifying composition, in which tetrahydrofuran (THF) is mixed with 1-chloroethylbenzene. [Diagram 5] 1 is a graph showing 1H-NMR measurements to confirm the reactivity during synthesis and deposition of a thin film modifying composition, in which ethyl alcohol is mixed with 1-chloroethylbenzene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0083] The vacuum-based thin film modifier, a thin film modifier composition containing the same, a thin film forming method using the same, and a semiconductor substrate manufactured thereby will be described in detail below.

[0084] In this description, the term "thin film modification" means, unless otherwise specified, controlling the surface of the substrate that is used as the surface chemical reaction surface in the deposition process.

[0085] In this description, the term "shielding" means, unless otherwise specified, not only reducing, preventing, or blocking the adsorption of precursor compounds for forming a thin film onto a substrate, but also reducing, preventing, or blocking process by-products from adsorbing onto a substrate.

[0086] The present inventors have found that by using a compound having a specific structure as a thin film modifier for modifying the surface of a substrate and improving the deposition or etching process during a vacuum-based deposition or etching process, the growth rate of the deposited film can be appropriately reduced, and even when a thin film is formed on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film can be significantly improved, and the efficiency of the etching film can be improved, and in particular, it is possible to deposit a thin thin film, and it is possible to improve 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. Based on this finding, the present invention has been completed by incorporating research into vacuum-based thin film modifiers.

[0087]

[0088] The vacuum-based thin film modifier of the present invention can be applied to a vacuum-based deposition film or a vacuum-based etching film.

[0089] The deposited or etched film may be provided as one or more precursors selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, for example, and may provide a modified region for an oxide film, a nitride film, a metal film, or a selective thin film thereof. In this case, the effect to be achieved in the present invention may be sufficiently obtained.

[0090] As a specific example, the thin film may have a film composition of a silicon oxide film or a silicon nitride film.

[0091] The thin film can be used in semiconductor devices not only as a commonly used diffusion barrier film, but also as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a blocking thin film, or a charge trap.

[0092]

[0093] In the present invention, as an example of a precursor compound used to form a thin film, a compound represented by the following chemical formula 2 can be used.

[0094] chemical formula 2

[0095] [ka]

[0096] (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 -H, -X, -R, -OR, -NR 2 or Cp (cyclopentadiene), which may be the same or different, where -X is F, Cl, Br, or I, and -R is C1-C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 can be formed to 2 to 6 depending on the oxidation value of the central metal.)

[0097] 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 , L2 , 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.

[0098] The M may be a type 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 tellurium (Ta). In this case, there are advantages in that there is a large effect of reducing process by-products, excellent step coverage, an effect of improving thin film density, and further excellent electrical properties, insulating properties, and dielectric properties of the thin film.

[0099] Said L 1 , L 2 , L 3 and L 4 is -R, -X or Cp, which may be the same or different, where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may have a linear or cyclic structure.

[0100] In addition, the above-mentioned L 1 , L 2 , L 3 and L 4 -NR 2 or Cp, which may be the same or different, where -R is H, C1-C10 alkyl, C1-C 10 Alkenes, C1-C 10 alkane, iPr, or tBu.

[0101] Furthermore, in the above-mentioned Chemical Formula 8, L 1 , L 2 , L 3 and L 4are -H, or -X, which may be the same or different from each other, where -X can be F, Cl, Br, or I.

[0102] Specifically, examples of aluminum precursor compounds that can be used include Al(CH3)3 and AlCl4.

[0103] Examples of hafnium precursor compounds that can be used include tris(dimethylamido)cyclopentadienylhafnium, CpHf(NMe2)3, and (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium, Cp(CH2)3NM3Hf(NMe2)2.

[0104] Examples of silicon precursor compounds that can be used include hexachlorodisilane (HCDS), dichlorosilane (DCS), tris(dimethylamino)silane (3DMAS), bis(diethylamino)silane (BDEAS), and octamethylcyclotetrasiloxane (OMCTS).

[0105] The vacuum-based thin film modifier of the present invention can control the growth of a vacuum-based thin film and control the film quality by reducing the rate at which the precursor compound is adsorbed onto the substrate, by previously controlling the surface of the substrate to which the precursor compound is adsorbed.

[0106] The vacuum-based thin film modifier may include an aromatic compound having a hydrocarbon group and a halogen group, which suppresses side reactions during deposition or etching film formation, controls the thin film growth rate, reduces process by-products in the thin film, reduces corrosion and deterioration, improves the crystallinity of the thin film, and minimizes impurity contamination while significantly improving step coverage and thin film thickness uniformity, even when the thin film is formed on a substrate having a complex structure.

[0107] As a specific example, the refractive index of the aromatic compound having a hydrocarbon group and a halogen group may be within the range of 1.50 to 1.60, 1.50 to 1.58, or 1.51 to 1.57. In this case, the effect of reducing process by-products is large, the step coverage is excellent, and the effect of improving the thin film density and the electrical properties of the thin film are further excellent.

[0108]

[0109] The vacuum-based thin film modifier contains a compound represented by the following formula 1, and thus has a large effect of reducing process by-products, excellent step coverage, and is further excellent in improving thin film density and electrical properties of the thin film.

[0110] chemical formula 1

[0111] [ka]

[0112] (In the above Chemical Formula 1, R', R" and X are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, and each contains at least one halogen group.)

[0113]

[0114] Specifically, R', R" and X may be hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively. In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties of the thin film are further excellent.

[0115]

[0116] When the thin film is a deposition film, the vacuum-based thin film modifier may be at least one selected from the compounds represented by the following chemical formulas 1-1 to 1-2. In this case, when the deposition film is formed, a relatively sparse thin film is formed, 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, not only can the step coverage and the film thickness uniformity of the thin film be significantly improved, but also impurity contamination can be minimized.

[0117] Chemical formula 1-1~1-2

[0118] [ka]

[0119] When the thin film is an etching film, the vacuum-based thin film modifier may be preferably a compound represented by the following chemical formulas 1 to 3, in which case the etching process can be effectively performed while minimizing contamination by impurities.

[0120] Chemical formula 1-3

[0121] [ka]

[0122] The above-mentioned vacuum-based thin film modifier can be used alone, but considering the harsh atmosphere under a vacuum base, it is preferable to use it in combination with a specific organic solvent, since this makes it possible to carry out the process more efficiently.

[0123] The organic solvent used here is preferably one having a dielectric constant of 15 or less, for example, since it does not affect the reaction mechanism of the vacuum-based thin film modifier under vacuum and can improve the process.

[0124] The organic solvent having a dielectric constant of 15 or less includes a hydrocarbon solvent or a heterocycle-containing solvent.

[0125] The hydrocarbon solvent may be a linear hydrocarbon compound having an alkyl group having 1 to 10 carbon atoms, and an example of the hydrocarbon solvent that can be used is octane (d: 1.9 at 25° C.).

[0126] The heterocycle-containing solvent may contain nitrogen or oxygen.

[0127] An example of the nitrogen-containing solvent is dimethylethylamine (d: 3.2 at 25° C.).

[0128] An example of the oxygen-containing solvent is tetrahydrofuran (d: 7.6 at 25° C.).

[0129]

[0130] As a specific example, the vacuum-based thin film modifying composition may include at least one compound selected from the compounds represented by the above formulas 1-1 to 1-3, and an organic solvent having a dielectric constant of 15 or less. In this case, the composition has a large effect of controlling the growth rate of the deposition film, a large effect of removing process by-products, and an excellent effect of improving step coverage and film quality. Even if applied to a substrate with a complex structure, the composition ensures the uniformity of the thin film and significantly improves step coverage. In particular, the composition can be deposited on a thin thin film, and can provide an effect of improving O, Si, metal, metal oxide, and even carbon residues that were difficult to reduce in the past, which can improve film quality even when an etched film is manufactured.

[0131] The reactive gas may include O2, NH3, or H2.

[0132] The thin film may be a thin film having one or more layers of one or more metals selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd laminated thereon.

[0133] The vacuum-based thin film modifier can provide modified regions for thin films.

[0134] The vacuum-based thin film modifier is characterized by not remaining in the thin film.

[0135] Here, unless otherwise specified, "not remaining" refers to the presence of C element less than 0.1 atomic % (atom %), Si element less than 0.1 atomic % (atom %), N element less than 0.1 atomic % (atom %), and halogen element less than 0.1 atomic % (atom %) in a component analysis by X-ray photoelectron spectroscopy (XPS). More preferably, in a measurement method by secondary ion mass spectrometry (SIMS) in which measurements are made while digging into the substrate in the depth direction, or a measurement method by X-ray photoelectron spectroscopy (XPS), when considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using a vacuum-based thin film modifier 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%.

[0136] As an example, the thin film may contain halogen compounds at 100 ppm or less.

[0137] 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 blocking thin film, or a charge trap, but is not limited thereto.

[0138] The vacuum-based thin film modifier, organic solvent and precursor compound may preferably be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, there is a risk that impurities will remain in the thin film or cause side reactions with the precursor or reactant, so it is preferable to use a material with a purity of 99% or more as much as possible.

[0139]

[0140] The vacuum-based thin film modifier is preferably used in an atomic layer deposition (ALD) process, and in this case, it has the advantages of being used as a vacuum-based thin film modifier without interfering with the adsorption of precursor compounds, effectively protecting the surface of the substrate, and effectively removing process by-products.

[0141] The vacuum-based thin film modifier is preferably liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20°C) may be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, the modified region is effectively formed, and there is an effect of excellent improvement in step coverage, thin film thickness uniformity, and film quality.

[0142] More preferably, the vacuum-based thin film modifier has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.3g / cm 3 The vapor pressure (20° C.) can be 1 to 260 mmHg. Within this range, the modified region is effectively formed, and there is an effect of excellent improvement in step coverage, thin film thickness uniformity, and film quality.

[0143] The vacuum-based thin film modifier is preferably used in an atomic layer etching (ALE) process, in which case, since chemical etching is used, it has the effect of realizing the selective etching and isotropic etching characteristics of the etched film to be provided.

[0144]

[0145] The thin film forming method of the present invention includes the steps of treating a surface of a substrate loaded in a chamber with the vacuum-based thin film modifying agent or the vacuum-based thin film modifying composition;

[0146] and sequentially injecting a precursor compound and a reactive gas into a chamber to form a vacuum-based deposited thin film on the substrate at 20 to 800°C and under a vacuum of less than 760 torr, the reactive gas being an oxidizing agent or a reducing agent. In this case, the deposition rate of the thin film on the substrate is reduced and the thin film growth rate is appropriately decreased, thereby significantly improving step coverage and thin film thickness uniformity while minimizing impurity contamination, even when a thin film is formed on a substrate having a complex structure.

[0147] In the step of treating with the vacuum-based thin film modifier or thin film modifier composition, the feeding time (seconds [sec]) of the vacuum-based thin film modifier or thin film modifier composition to the surface of the substrate is preferably 0.01 to 10 seconds per cycle, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 5 seconds. Within this range, there are advantages in that not only is the thin film growth rate low, and excellent step coverage and economy are achieved, but also impurity contamination can be minimized.

[0148] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle in a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle in a chamber volume of 18 L.

[0149]

[0150] The thin film modification method of the present invention may include the steps of i) vaporizing the vacuum-based thin film modifier or thin film modification composition to form a modified region on the surface of a substrate loaded into a chamber, and ii) first purging the inside of the chamber with a purge gas.

[0151] As a preferred embodiment, the thin film modification method and further the thin film formation method may include the steps of: i) vaporizing the vacuum-based thin film modifier or thin film modification composition and applying it to a surface of a substrate loaded into a chamber; ii) first purging the interior of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it onto the surface of the substrate loaded into the chamber; iv) second purging the interior of the chamber with a purge gas; v) supplying a reaction gas into the chamber; and vi) third purging the interior of the chamber with a purge gas.

[0152] In this case, steps i) to vi) can be considered as a unit cycle and the cycle can be repeated until a thin film having a desired thickness is obtained. In this manner, when the vacuum-based thin film modifier or thin film modifier composition of the present invention is added prior to the precursor compound in one cycle and adsorbed onto the substrate, even if deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, the process by-products generated can be effectively removed, the resistivity of the thin film can be reduced, and the step coverage can be significantly improved.

[0153] In another preferred embodiment, the substrate may be manufactured by applying the vacuum-based thin film modifier to a substrate loaded in a chamber under a temperature condition of 20 to 800°C.

[0154] As a preferred example of the thin film formation method of the present invention, the vacuum-based thin film modifier or thin film modifier composition of the present invention can be added prior to a precursor compound in one cycle to activate the surface of a substrate, and then the precursor compound can be added and adsorbed onto the substrate. In this case, even if the thin film is deposited at a high temperature, the thin film growth rate can be appropriately reduced, so that process by-products can be significantly reduced, step coverage can be significantly improved, and the crystallinity of the thin film can be increased to reduce the resistivity of the thin film. Even if the thin film is applied to a semiconductor device with a large aspect ratio, the uniformity of the thin film thickness can be significantly improved, ensuring the reliability of the semiconductor device.

[0155]

[0156] In the thin film formation method, for example, when the precursor compound is deposited before or after deposition of the precursor compound, a unit cycle can be repeated 1 to 99,999 times as necessary, and preferably a unit cycle can be repeated 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the effect to be achieved in the present invention can be sufficiently obtained while obtaining the desired thin film thickness.

[0157]

[0158] The precursor compound is a molecule having one or more central metal atoms (M) selected from the group consisting of Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and one or more ligands consisting of C, N, O, H, X (halogen), and Cp (cyclopentadiene). In the case of a precursor having a vapor pressure of 1 mTorr to 100 torr at 25° C., the effect of forming a modified region by the vacuum-based thin film modifier or thin film modifier composition can be maximized despite natural oxidation.

[0159] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

[0160] The thin film may be a silicon oxide film, a silicon nitride film, a titanium oxide film, a titanium nitride film, a hafnium oxide film, a hafnium nitride film, a zirconium oxide film, a zirconium nitride film, a tungsten oxide film, a tungsten nitride film, an aluminum oxide film, an aluminum nitride film, a niobium oxide film, a niobium nitride film, a tellurium oxide film, or a tellurium nitride film.

[0161] In the present invention, the precursor compound or the precursor compound may include a step of plasma post-treatment after being vaporized and injected, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0162]

[0163] In the case where the vacuum-based thin film modifier or thin film modifier composition is first adsorbed on a substrate, the precursor compound is then adsorbed, and the precursor compound is then adsorbed, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed thin film modifier or thin film modifier composition is not particularly limited as long as it is an amount sufficient to remove the unadsorbed vacuum-based thin film modifier or thin film modifier composition, but as an example, it 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 modifier or thin film modifier composition can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of the purge gas, vacuum-based thin film modifier, and thin film modifier composition introduced are based on one cycle, and the volumes of the vacuum-based thin film modifier and thin film modifier composition refer to the volume of the vaporized vacuum-based thin film modifier or thin film modifier composition.

[0164] As a specific example, when the injection amount of the vacuum-based thin film modifier or thin film modifier composition is 200 sccm and the purge gas has a flow rate of 5000 sccm in the step of purging the unadsorbed vacuum-based thin film modifier or thin film modifier composition, the injection amount of the purge gas is 25 times the injection amount of the vacuum-based thin film modifier or thin film modifier composition.

[0165]

[0166] 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, more preferably 100 to 10,000 times based on the volume of the precursor compound introduced into the chamber, and within this range, the unadsorbed precursor compound can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound means the volume of the vaporized precursor compound vapor.

[0167]

[0168] 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.

[0169]

[0170] The vacuum-based thin film modifier, thin film modifier composition and precursor compound can be preferably delivered into the chamber by a VFC method, a DLI method or an LDS method, and more preferably delivered into the chamber by an LDS method.

[0171] The substrate loaded in the chamber may be heated to, for example, 100 to 650°C, specifically, 150 to 550°C, and the vacuum-based thin film modifier, thin film modifier composition, or precursor compound may be injected onto the substrate in an unheated or heated state, and depending on deposition efficiency, the heating conditions may be adjusted during the deposition process after being injected unheated. For example, the substrate may be injected at 100 to 650°C for 1 to 20 seconds.

[0172]

[0173] The ratio (mg / cycle) of the precursor compound to the vacuum-based thin film modifier or thin film modifier composition 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.

[0174]

[0175] In the thin film formation method, for example, when the vacuum-based thin film modifier or thin film modifier composition and the precursor compound are used, the deposition rate reduction rate represented by the following mathematical formula 1 may be 15% or more, specifically 18% or more, and preferably 21% or more. In this case, a relatively sparse thin film is formed using the vacuum-based thin film modifier or thin film modifier composition having the above structure, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the method is applied to a substrate having a complex structure under high temperature, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the thin film can be deposited at a thin thickness, and the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was previously difficult to reduce, can be improved.

[0176] Formula 1

[0177]

number

[0178] (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 a thin film formed without the addition of a vacuum-based thin film modifier or thin film modifier composition. DR f (final deposition rate) is the deposition rate of a thin film formed by introducing a vacuum-based thin film modifier or thin film modifier composition when carrying out the above-mentioned process. Here, the deposition rate (DR) is a 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.

[0179] In Equation 1, the thin film growth rate per cycle when a vacuum-based thin film modifier or thin film modifier composition is used and when it is not used means the deposition thickness (Å) of the thin film per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by dividing the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure by the total number of cycles to obtain an average deposition rate.

[0180] In the above formula 1, "when no vacuum-based thin film modifier or thin film modifier composition was used" refers to a case where a thin film is manufactured by adsorbing only a precursor compound onto a substrate during a thin film deposition process. A specific example of the thin film formation method is a case where a thin film is formed by omitting the step of adsorbing a vacuum-based thin film modifier or thin film modifier composition and the step of purging unadsorbed vacuum-based thin film modifier or thin film modifier composition.

[0181]

[0182] In the thin film formation method, the strength (c / s) of residual halogen in the thin film based on a film thickness of 100 Å, as 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.

[0183] 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.

[0184]

[0185] 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.

[0186] 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 300 to 700°C, more preferably at a deposition temperature in the range of 400 to 650°C, even more preferably at a deposition temperature in the range of 400 to 600°C, and even more preferably at a deposition temperature in the range of 450 to 600°C. Within this range, there is an effect of growing a thin film with excellent film quality while realizing the ALD process characteristics.

[0187] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 torr to 20 torr, preferably at a deposition pressure in the range of 0.1 torr to 20 torr, more preferably at a deposition pressure in the range of 0.1 torr to 10 torr, and most preferably at a deposition pressure in the range of 0.3 torr to 7 Torr. Within this range, there is an effect that a thin film with a uniform thickness can be obtained.

[0188] 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.

[0189] The thin film formation method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the precursor compound into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the precursor compound into the chamber.

[0190] The present invention may also include a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, the thin film manufacturing apparatus including an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transport means for transporting the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing the thin film precursor, and a second transport means for transporting the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and the transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the technical field to which the present invention pertains.

[0191] The heating temperature of the deposition transport means (hereinafter referred to as the "injection line") may be in the range of 25 to 200°C for the substrate, and the reaction gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

[0192]

[0193] According to another aspect of the present invention, there can be provided a method for forming a thin film, comprising the steps of: treating a surface of a substrate loaded into a chamber with the vacuum-based thin film modifier or the vacuum-based thin film modifier composition; and injecting an etching material into the chamber to form a vacuum-based etching film on the substrate, wherein the etching material is one or more selected from the group consisting of Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0194] The etching material may be a mixture of Ar, H2, or O2, and other than this, details that overlap with the formation of the deposition film will be omitted.

[0195]

[0196] 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.

[0197] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 0.5 to 20 nm, more preferably 1.5 to 15 nm, and even more preferably 2 to 10 nm. Within this range, the thin film has excellent thin film properties.

[0198] The thin film may have a carbon impurity content of preferably 5,000 counts / sec or less or 1 to 3,000 counts / sec, more preferably 10 to 1,000 counts / sec, and even more preferably 50 to 500 counts / sec. Within this range, there is an effect that the thin film growth rate is reduced while the thin film properties are excellent.

[0199] 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.

[0200] The thin film thus produced preferably has a thickness of 20 nm or less, a dielectric constant of 5 to 29 based on a thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage rate of 90% or more. Within these ranges, the thin film has the effect of having excellent performance as a dielectric film or a blocking film, but is not limited thereto.

[0201]

[0202] The thin film may have a multilayer structure of two or more layers, preferably two or three layers, as required. 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.

[0203] The underlayer film may, for example, comprise one or more selected from the group consisting of Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0204] The intermediate layer is, for example, Ti x N y , preferably TN.

[0205] The upper layer film may contain, for example, one or more selected from the group consisting of W and Mo.

[0206] 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.

[0207]

[0208] Below, preferred embodiments and drawings are presented to aid in understanding the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the technical spirit thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0209]

[0210] EXAMPLES

[0211] Examples 1-2, Comparative Example 1

[0212] The ALD deposition process was carried out using the components and process conditions shown in Tables 1 and 2 below.

[0213] Specifically, in Table 1 below, for the deposition of SiN in Comparative Example 1, a hexachlorodisilane (HCDS) precursor was used, the canister heating temperature was 35°C, the N2 carrier gas flow rate was 40 sccm injected for 3 seconds, the NH3 flow rate was 1000 sccm injected for 30 seconds, and the N2 purge gas flow rate was 1000 sccm injected for 12 seconds, and 100 to 150 cycles were repeated.

[0214]

[0215] In Table 1 below, for the SiN deposition in Example 1, a material represented by the following Chemical Formula 1-1 with a purity of 99.6% was used.

[0216] Chemical formula 1-1

[0217] [ka]

[0218] At this time, the conditions were maintained such that the canister heating temperature was 50° C., and the N2 carrier gas flow rate was 100 sccm for 3 seconds. In addition, the process of injecting the substance represented by the chemical formula 1-1 for 3 seconds was repeated 100 to 150 cycles.

[0219]

[0220] For the SiN experiment of Example 2 in Table 1 below, the material represented by Chemical Formula 1-1 and the organic solvent represented by Chemical Formula 3-1 below were mixed in a 1:1 molar ratio, and a liquid delivery system (LDS) was used to inject the material at 0.1 g / min for 3 seconds. The same procedure as in the SiN experiment of Example 1 was repeated.

[0221] Chemical formula 3-1

[0222] [ka]

[0223] For the thin films obtained in Comparative Example 1 and Examples 1 and 2, the thickness of the 10 nm SiN thin film was analyzed by optical ellipsometry, and the deposition rate was measured.

[0224] *XPS depth analysis: An elemental depth analysis was performed by Ar sputtering using an X-ray photoelectron spectroscopy (XPS, ESCALAB 200R, VG Scientific) device with an Al Kα X-ray source to confirm the presence or absence of residual C in the SiN thin film obtained in Example 2, and the results are shown in Figure 1 below.

[0225] *Deposition rate measurement: The thickness of a 10 nm-thick SiN thin film was measured by ellipsometry optical analysis fitting, and the deposition rate of the film thickness per cycle was measured by dividing the measured thickness by the total ALD cycle. The reduction rate was calculated using Equation 1, and the results are shown in Table 1 below.

[0226] Formula 1

[0227]

number

[0228] [Table 1]

[0229] As shown in Table 1, in the case of Example 1 using the vacuum thin film modifier according to the present invention, the reduction rate of the deposition rate reached -22% compared to Comparative Example 1 not using the vacuum thin film modifier. Also, as shown in Table 1, in the case of Example 2 using the vacuum thin film modifier composition according to the present invention, the reduction rate of the deposition rate reached -30% compared to Comparative Example 1 not using the vacuum thin film modifier. Furthermore, as shown in FIG. 2 below, in Example 2 using the vacuum thin film modifier composition according to the present invention, as the sputtering time increases, the depth shows elemental information from the surface to the inside, and the composition of the thin film was confirmed, and it was confirmed that carbon contamination was at a detection limit level of less than 0.1%.

[0230]

[0231] Examples 2 to 4, Comparative Example 2

[0232] The same process as in Example 2 was repeated, except that the compound represented by Chemical Formula 3-1 used in Example 2 was replaced with compounds represented by the following Chemical Formulas 3-2, 3-3, and 3-4, respectively, to prepare 10 nm SiN thin films. For reference, Chemical Formula 3-2 corresponds to Example 2, Chemical Formula 3-3 corresponds to Example 3, and Chemical Formula 3-4 corresponds to Comparative Example 2, respectively.

[0233] Chemical formula 3-2

[0234] [ka]

[0235] Chemical formula 3-3

[0236] [ka]

[0237] Chemical formula 3-4

[0238] [ka]

[0239] Specifically, for this experiment, among solvents having a dielectric constant of less than 15, the compound represented by the formula 3-1 (d at 25° C.: 1.9), the compound represented by the formula 3-2 (d at 25° C.: 3.7), the compound represented by the formula 3-3 (d at 25° C.: 7.6), and the compound represented by the formula 3-4 (d at 25° C.: 24.5) were mixed with the compound represented by the formula 1-1 in a molar ratio of 1:1, 1The degree of reactivity was confirmed by the presence or absence of new impurity peaks using H-NMR, and the results obtained are summarized in Table 2 and Figures 2 to 5. Here, when a new impurity peak was observed, it was determined that there was reactivity and was indicated by O, and when no new impurity peak was observed, it was determined that there was no reactivity and was indicated by ×.

[0240] [Table 2]

[0241] As shown in Table 2 and Figures 2 to 5, in the case of Examples 2 to 4 in which the compounds represented by the chemical formulas 3-1, 3-2, and 3-3 having a dielectric constant of 15 or less were blended, no reactivity with the vacuum thin film modifier to be used was observed, and it was judged to be effective in improving the deposition process. On the other hand, in the case of Comparative Example 2 in which the compound represented by the chemical formula 3-4 having a dielectric constant of more than 15 was blended, it was observed to be reactive with the vacuum thin film modifier to be used, and it was judged to be unsuitable for improving the deposition process.

Claims

1. A vacuum-based thin film modifier comprising an aromatic compound having a hydrocarbon group and a halogen group, for controlling the growth or film quality of a vacuum-based thin film formed from a precursor compound.

2. The vacuum-based thin film modifier according to claim 1 , wherein the vacuum-based thin film is a vacuum-based deposition film or a vacuum-based etching film.

3. The vacuum-based thin film modifier according to claim 1 , wherein the aromatic compound having a hydrocarbon group and a halogen group includes a compound represented by the following Chemical Formula 1: Chemical formula 1 【Chemistry 1】 (In the above Chemical Formula 1, R', R" and X are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkene group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, and each contains at least one halogen group.)

4. The vacuum-based thin film modifier according to claim 3, wherein in Formula 1, R', R" and X are hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively.

5. The vacuum-based thin film modifier according to claim 1, wherein the aromatic compound having a hydrocarbon group and a halogen group has a refractive index of 1.50 to 1.

60.

6. The vacuum-based thin film modifier according to claim 1, wherein the vacuum-based thin film modifier comprises a compound represented by the following chemical formulas 1-1 to 1-2 when the thin film is a deposition film, and comprises a compound represented by the following chemical formula 1-3 when the thin film is an etching film. Chemical formulas 1-1 to 1-3 【Chemistry 2】

7. A vacuum-based thin film modifying composition comprising the vacuum-based thin film modifying agent according to any one of claims 1 to 6 and an organic solvent having a dielectric constant of 15 or less.

8. The vacuum-based thin film modifying composition according to claim 7, wherein the organic solvent having a dielectric constant of 15 or less is a hydrocarbon solvent or a heterocycle-containing solvent.

9. 8. The vacuum-based thin film modifying composition of claim 7, wherein the organic solvent having a dielectric constant of 15 or less is octane, dimethylethylamine or tetrahydrofuran.

10. Treating a surface of a substrate loaded into a chamber with a vacuum-based thin film modifier as claimed in claim 1 or a vacuum-based thin film modifier composition as claimed in claim 7; sequentially injecting a precursor compound and a reactant gas into a chamber to form a vacuum-based deposited thin film on the substrate at 20-800° C. and a vacuum of less than 760 torr; Including, The thin film forming method, wherein the reactive gas is an oxidizing agent or a reducing agent.

11. Treating a surface of a substrate loaded into a chamber with a vacuum-based thin film modifier as claimed in claim 1 or a vacuum-based thin film modifier composition as claimed in claim 7; injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate; Including, The etching material is Cl ２ , CCl ４ , C.F. ２ C ２ , C.F. ３ Cl, CF ４ , C.H.F. ３ , C ２ F ６ , S.F. ６ , BCl ３ , B ２ , and C.F. ３ Br.

12. 12. The method of claim 10 or 11, wherein the chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber or a plasma enhanced chemical vapor deposition (PECVD) chamber.

13. The method of claim 10, wherein the vacuum-based thin film modifier, the vacuum-based thin film modifier composition, and the precursor compound are delivered into the chamber by a VFC (vapor flow control) method, a DLI (direct liquid introduction) method, or an LDS (liquid delivery system) method, and the heating temperature of the injection line is 25 to 200° C. on the substrate.

14. The etching material is Ar, H ２ , or O ２ The method for forming a thin film according to claim 11, wherein the thin film is used in combination with

15. A semiconductor substrate comprising a thin film produced by the thin film formation method according to claim 10 or 11.

16. 16. The semiconductor substrate according to claim 15, wherein the thin film has a multi-layer structure of two or more layers.

17. A semiconductor device comprising the semiconductor substrate of claim 15.

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