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

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 formation method using the same, and semiconductor substrates and semiconductor devices manufactured therein. More specifically, the present invention provides a vacuum-based thin film modifier containing a compound of a predetermined structure, which appropriately reduces the growth rate of the deposited film during the vacuum-based thin film process, thereby significantly improving step coverage and the uniformity of the film thickness, even when forming a thin film on a substrate with a complex structure, improving the efficiency of the etching film, and significantly reducing contamination by impurities such as carbon. The present invention relates to a vacuum-based thin film modifier, a thin film modifier composition containing the same, a thin film formation method using the same, and semiconductor substrates manufactured therein. [Background technology]

[0002] As the integration density of memory and non-memory semiconductor elements increases, the microstructure of substrates is becoming increasingly complex.

[0003] For example, the ratio of the width to the depth of the microstructure (hereinafter also called the "aspect ratio (length / width ratio)") has been increasing to 20:1 or more, and 100:1 or more. The larger the aspect ratio, the more difficult it becomes to form a deposit with a uniform thickness along the complex microstructure surface.

[0004] As a result, the step coverage, which limits the thickness ratio of the deposited layers formed in the upper and lower parts of the microstructure in the depth direction, remains at a level of 90%, making it increasingly difficult for the electrical characteristics of the device to be expressed. Since 100% step coverage means that the thickness of the deposited layers formed in the upper and lower parts of the microstructure is the same, it is necessary to develop technology to make the step coverage as close to 100% as possible.

[0005] The thin film for semiconductors consists of a nitride film, a thin film, a metal film, and the like. Examples of nitride films include silicon nitride (SiN), titanium nitride (TiN), and tantalum nitride (TaN); examples of thin films include silicon oxide (SiO2), hafnium oxide (HfO2), and zirconium oxide (ZrO2); and examples of metal films include molybdenum film (Mo) and tungsten (W).

[0006] The aforementioned thin film is generally used as a diffusion barrier between the doped silicon layer of a semiconductor and interlayer wiring materials such as aluminum (Al) and copper (Cu). However, when a tungsten (W) thin film is deposited onto a substrate, it is used as an adhesion layer.

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

[0008] When increasing the deposition temperature to achieve 100% step coverage, difficulties arise in achieving step coverage. First, in a deposition process consisting of two types of materials, a precursor and a reactant, increasing the deposition temperature not only leads to a steep increase in the thin film growth rate (GPC: Growth Per Cycle), but even if the ALD process is performed at 300°C to mitigate the increase in GPC due to the increased deposition temperature, the deposition temperature will still increase during the process, making it difficult to call this a solution.

[0009] In addition, in order to realize a metal thin film with excellent film quality in a semiconductor device, a high-temperature process is required. Research results have been reported that increasing the atomic layer deposition temperature to 400 °C reduces the concentrations of carbon and hydrogen remaining in the thin film (see the paper in J.Vac.Sci.Technol.A, 35(2017)01B130).

[0010] However, the higher the deposition temperature, the more difficult it is to ensure the step coverage rate. First, in the deposition process composed of two types of precursors and reactants, an increase in the deposition temperature may lead to a sharp increase in the growth rate per cycle (GPC) of the thin film. Also, in order to mitigate the increase in GPC due to the increase in deposition temperature, even if a known masking agent is applied, it has been confirmed that the GPC increases by about 10% at 300 °C. That is, when depositing at 360 °C or higher, it is difficult to expect the GPC reduction effect provided by the conventionally known masking agent.

[0011] Therefore, there is a current need for the development of a thin film formation method that can effectively form a thin film with a complex structure even at high temperatures, with a low residual amount of impurities, and that can significantly improve the step coverage and the film thickness uniformity of the thin film, as well as a semiconductor substrate manufactured thereby. <000008​​​​​​​​​​​​The object of the present invention is to improve the density and dielectric properties of a thin film by improving the crystallinity and oxidation fraction of the thin film.

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

Means for Solving the Problems

[0015] In order to achieve the above object, the present invention provides a vacuum-based thin film modifier characterized by including an aromatic compound having a hydrocarbon group and a halogen group and 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 vapor deposition film or a vacuum-based etching 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]

Chemical

[0020] <000012k> (In 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 include at least one halogen group.)

[0021] In Chemical Formula 1, R’, R” and X can each be hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively.

[0022] [[ID=J3]]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] The vacuum-based thin-film modifier may, when the thin film is a deposited film, contain compounds represented by the following chemical formulas 1-1 to 1-2.

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

[0025] [ka]

[0026] The vacuum-based thin-film modifier may, when the thin film is an etched film, contain 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 reaction surface of the thin film formed from the silane precursor compound.

[0030]

[0031] Furthermore, the present invention is

[0032] The present invention provides a vacuum-based thin film modifier and a vacuum-based thin film modifier comprising an organic solvent having a dielectric constant of 15 or less.

[0033]

[0034] The aforementioned organic solvent with a dielectric constant of 15 or less may be a hydrocarbon solvent or a heterocyclic solvent.

[0035] The organic solvents with a dielectric constant of 15 or less are octane, dimethylethylamine, or tetrahydrofuran.

[0036]

[0037] Furthermore, the present invention is

[0038] The process involves treating the surface of a substrate loaded into a chamber with the aforementioned vacuum-based thin film modifier or vacuum-based thin film modifier composition,

[0039] The present invention provides a thin film formation method comprising the steps of sequentially injecting a precursor compound and a reaction gas into a chamber to form a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and a vacuum of less than 760 torr, wherein the reaction 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 can be transported into the chamber by a vapor flow control (VFC), direct liquid introduction (DLI), or liquid delivery system (LDS).

[0042] At this time, the heating temperature of the deposition transport line (hereinafter referred to as the "injection line") may be in 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 reaction gas may include O2, O3, N2O, NO2, H2O, or O2 plasma.

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

[0046] The thin film may be used as a diffusion prevention film, etching stop film, electrode film, dielectric film, gate insulating film, blocking thin film, or charge trap.

[0047]

[0048] Furthermore, the present invention is

[0049] The steps include treating the surface of a substrate loaded into a chamber with the aforementioned vacuum-based thin film modifier or vacuum-based thin film modifier composition,

[0050] The step includes injecting an etching material into a chamber to form a vacuum-based etching film on a substrate, The present invention provides a thin film formation method characterized in that the etching material is one or more selected from Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0051] The chamber may 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 transported into the chamber by VFC, DLI, or LDS.

[0053] The etching material can be used in combination with Ar, H2, or O2.

[0054]

[0055] The aforementioned thin film modification method is

[0056] i) A step of vaporizing the aforementioned vacuum-based thin film modifier or thin film modifier composition to form a modified region on the surface of a substrate loaded into a chamber,

[0057] ii) The method is characterized by comprising the step of primary purging the inside of the chamber with a purge gas.

[0058]

[0059] The thin film formation method described above is

[0060] i) A step of vaporizing the aforementioned vacuum-based thin film modifier or thin film modifier composition to form a modified region on the surface of a substrate loaded into a chamber,

[0061] ii) A step of primary purging the inside of the chamber with a purge gas,

[0062] iii) A step of vaporizing the precursor compound and adsorbing it onto the region outside the modified region,

[0063] iv) The step of secondary purging the inside of the chamber with purge gas,

[0064] v) The step of supplying a reaction gas to the inside of the chamber,

[0065] vi) A thin film formation method is provided, characterized by comprising the step of tertiarily 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 supplied by coating a substrate loaded into a chamber under temperature conditions of 20 to 800°C.

[0068] The precursor compound is 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 greater than 0.01 mTorr and less than or equal to 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 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 reaction gas is an oxidizing agent or a reducing agent, and the reaction gas, vacuum-based thin-film modifier, thin-film modifier composition, and precursor compound can be transported into the chamber by VFC, DLI, or LDS.

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

[0073]

[0074] Furthermore, the present invention provides a semiconductor substrate characterized by including a thin film manufactured by the thin film formation method described above.

[0075] The thin film may have a multilayer structure consisting of two or three or more layers.

[0076] Furthermore, the present invention provides a semiconductor device including the aforementioned semiconductor substrate.

[0077] The semiconductor substrate may be a low-resistive metal gate interconnect, a high-aspect-ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA) capacitor, or a 3D NAND flash memory. [Effects of the Invention]

[0078] The present invention provides a vacuum-based thin film modifier or thin film modifying composition that can appropriately reduce the thin film growth rate during vacuum-based thin film processes, significantly improving step coverage and thin film thickness uniformity even when forming thin films on substrates with complex structures, and significantly reducing contamination by impurities such as carbon.

[0079] Furthermore, the process by-products during thin film formation are more effectively reduced, preventing corrosion and degradation, and improving the crystallinity of the thin film by modifying its properties, thereby improving its electrical properties.

[0080] Furthermore, by reducing process by-products, lowering the reaction rate, and appropriately decreasing the thin film growth rate during thin film formation, it is possible to improve step coverage and thin film density even when forming thin films on substrates with complex structures. Moreover, it is possible to provide a thin film formation method using this method and a semiconductor substrate manufactured therefrom. [Brief explanation of the drawing]

[0081] [Figure 1] This figure shows the results of XPS depth analysis of a 10 nm thick SiN thin film produced using the thin film modification composition according to the present invention, confirming the presence or absence of carbon residue within the thin film.

[0082] [Figure 2] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of a thin-film modification composition, specifically the case where octane is mixed with 1-chloroethylbenzene. [Figure 3] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of a thin-film modification composition, specifically the case where dimethylethylamine (DMEA) is mixed with 1-chloroethylbenzene. [Figure 4] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of a thin-film modification composition, specifically the case where tetrahydrofuran (THF) is mixed with 1-chloroethylbenzene. [Figure 5] This graph shows 1H-NMR measurements taken to confirm the reactivity during the synthesis and deposition of a thin-film modification composition, specifically the case where ethyl alcohol is mixed with 1-chloroethylbenzene. [Modes for carrying out the invention]

[0083] The following describes in detail the vacuum-based thin-film modifier described herein, the thin-film modifier composition containing the same, the thin-film formation method using the same, and the semiconductor substrate manufactured therefrom.

[0084] In this description, unless otherwise specified, the term "thin film modification" refers to the control of the surface of the substrate used as the surface chemical reaction surface in the vapor deposition process.

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

[0086] The inventors have found that by using a compound with a predetermined structure as a thin film modifier to modify the surface of a substrate during a vacuum-based deposition or etching process, and by appropriately reducing the growth rate of the deposited film, it is possible to significantly improve step coverage and the uniformity of the film thickness, even when forming a thin film on a substrate with a complex structure, thereby improving the efficiency of the etching film. In particular, it is possible to deposit thin films, and it is possible to improve residual O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce as by-products of the process. Based on this finding, the inventors incorporated this into their research on vacuum-based thin film modifiers and completed the present invention.

[0087]

[0088] The vacuum-based thin film modifier of the present invention may be applied to vacuum-based deposited films or vacuum-based etched films.

[0089] The aforementioned deposited film or etched film can be provided, for example, 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, and can provide a modification region for oxide films, nitride films, metal films, or selective thin films thereof, in which case the effects to be achieved in the present invention can be fully obtained.

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

[0091] The thin film can be utilized in semiconductor devices not only as a commonly used anti-reflection film but also for applications such 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 the precursor compound used to form the thin film, a compound represented by the following Chemical Formula 2 can be used.

[0094] Chemical Formula 2

[0095]

Chem.

[0096] (In the above Chemical Formula 2, M is one or more selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, La, Ce, and Nd, and L 1 , L 2 , L 3 and L 4 are -H, -X, -R, -OR, -NR 2 or Cp (cyclopentadiene), and they may be the same or different from each other. Here, -X is F, Cl, Br, or I, -R is an alkyl of C1 - C 10 , an alkene of C1 - C 10 , or an alkane of C1 - C 10 , which can be linear or cyclic. The L 1 , L 2 , L 3 and L 4 can be formed to be 2 - 6 according to the oxidation state 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 ligands. When the central metal is hexavalent, L 1 , L2 , L 3 , L 4 , L 5 , L 6 It can be attached to the central metal, L 1 ~L 6 The ligands corresponding to these may be the same or different from each other.

[0098] The aforementioned M may be of a type corresponding to a trivalent metal, tetravalent metal, pentavalent metal, or hexavalent metal, and is preferably hafnium (Hf), zirconium (Zr), aluminum (Al), niobium (Nb), or tellurium (Ta). In this case, there is a significant effect in reducing process by-products, excellent step coverage, and further advantages in improving thin film density, electrical properties, insulation, and dielectric properties of the thin film.

[0099] Said L 1 , L 2 , L 3 and L 4 -R, -X, or Cp, which may be the same or different from each other, where -R is C1~C 10 Alkyl, C1~C 10 Alkenes of the C1-C 10 It is an alkane, which may have a linear or cyclic structure.

[0100] Furthermore, the L 1 , L 2 , L 3 and L 4 -NR 2 or Cp, which may be the same or different from each other, where -R is H, C1-C10 alkyl, C1-C 10 Alkenes, C1~C 10 It could be an alkane, iPr, or tBu.

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

[0102] Specifically, suitable aluminum precursor compounds include, for example, Al(CH3)3 and AlCl4.

[0103] Examples of hafnium precursor compounds that can be used include tris(dimethylamide)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 the film quality by pre-controlling the surface on the substrate where the precursor compound should be adsorbed, thereby reducing the rate at which the precursor compound is adsorbed onto the substrate.

[0106] The vacuum-based thin-film modifier may contain aromatic compounds having hydrocarbon and halogen groups. In such cases, side reactions are suppressed during the formation of deposited or etched films, the thin-film growth rate is adjusted, process by-products within the thin film are reduced, corrosion and degradation are reduced, the crystallinity of the thin film is improved, and even when forming a thin film on a substrate with a complex structure, impurity contamination is minimized while significantly improving step coverage and thickness uniformity of the thin film.

[0107] As a specific example, the aromatic compound having the hydrocarbon group and the halogen group may have a refractive index in 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 significant, the step coverage is excellent, and the effect of improving thin film density and the electrical properties of the thin film are even better.

[0108]

[0109] The vacuum-based thin-film modifier, by containing the compound represented by the following chemical formula 1, exhibits a significant reduction in process by-products, excellent step coverage, and further superior effects in improving thin-film density and the electrical properties of the thin film.

[0110] chemical formula 1

[0111] [ka]

[0112] (In the above chemical formula 1, R', R'', and X are independently selected from hydrogen, a C1-C5 alkyl group, a C1-C5 alkene group, a C1-C5 alkoxy group, and a halogen group, and each contains at least one halogen group.)

[0113]

[0114] As a specific example, R', R'', and X can be hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively. In this case, there is a significant reduction in process by-products, excellent step coverage, and further advantages in terms of improved thin film density and electrical properties of the thin film.

[0115]

[0116] The vacuum-based thin film modifier, when the thin film is a deposited film, is preferably one or more compounds selected from those represented by the following chemical formulas 1-1 to 1-2. In this case, when forming a deposited film, a relatively sparse thin film is formed, side reactions are suppressed, the thin film growth rate is adjusted, process by-products within the thin film are reduced, corrosion and degradation are reduced, the crystallinity of the thin film is improved, and even when forming a thin film on a substrate with a complex structure, not only are step coverage and thickness uniformity of the thin film greatly improved, but contamination by impurities can also be minimized.

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

[0118] [ka]

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

[0120] Chemical formula 1-3

[0121] [ka]

[0122] While the aforementioned vacuum-based thin-film modifiers can be used alone, considering the harsh atmosphere under vacuum conditions, it is preferable to use them in combination with specific organic solvents to carry out the process more efficiently.

[0123] The organic solvent used here is preferably one with a dielectric constant of 15 or less, as this does not affect the reaction mechanism under vacuum of the aforementioned vacuum-based thin-film modifier and improves the process.

[0124] Examples of organic solvents having a dielectric constant of 15 or less include hydrocarbon solvents and heterocyclic solvents.

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

[0126] The heterocyclic solvent may contain nitrogen or oxygen.

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

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

[0129]

[0130] As a specific example, the vacuum-based thin film modification composition may contain one or more compounds selected from the compounds represented by the aforementioned chemical formulas 1-1 to 1-3, along with an organic solvent having a dielectric constant of 15 or less. In this case, it has a significant effect in adjusting the growth rate of the deposited film, a significant effect in removing process by-products, and outstanding effects in improving step coverage and film quality. Moreover, even when applied to substrates with complex structures, it ensures thin film uniformity and greatly improves step coverage. In particular, it can be deposited on thin films and can improve residual O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce. Even when manufacturing etched films, it can provide an improvement in film quality.

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

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

[0133] The vacuum-based thin-film modifier can provide a modification region for thin films.

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

[0135] Here, "no residue" means, unless otherwise specified, the presence of C, Si, N, and halogen elements in amounts less than 0.1 atoms (atom%) during component analysis by X-ray photoelectron spectroscopy (XPS). More preferably, in a measurement method using secondary-ion mass spectrometry (SIMS) or X-ray photoelectron spectroscopy (XPS) while measuring while drilling into the substrate in the depth direction, when considering the increase or decrease in 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 or decrease in the signal intensity of each element species does not exceed 5%.

[0136] The thin film may, for example, contain a halogen compound at a concentration of 100 ppm or less.

[0137] The thin film can be used, but is not limited to, as a diffusion prevention film, etching stop film, electrode film, dielectric film, gate insulating film, blocking thin film, or charge trap.

[0138] The vacuum-based thin-film modifier, organic solvent, and precursor compound may preferably be a compound with a purity of 99.9% or higher, a compound with a purity of 99.95% or higher, or a compound with a purity of 99.99% or higher. For reference, if a compound with a purity of less than 99% is used, there is a risk that impurities may remain in the thin film or that side reactions may occur with the precursor or reactants. Therefore, it is preferable to use a substance with a purity of 99% or higher whenever possible.

[0139]

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

[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 / cm³. 3 Or 0.8~1.5 g / cm³ 3 The vapor pressure (at 20°C) can be between 0.1 and 300 mmHg or between 1 and 300 mmHg. Within this range, it effectively forms a modified region, resulting in excellent improvement of 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 / cm³. 3 Or 0.8-1.3 g / cm³ 3 The vapor pressure (at 20°C) can range from 1 to 260 mmHg, and within this range, it effectively forms a modified region, resulting in excellent step coverage, thin film thickness uniformity, and film quality improvement.

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

[0144]

[0145] The thin film formation method of the present invention comprises the steps of treating the surface of a substrate loaded into a chamber with the aforementioned vacuum-based thin film modifier or vacuum-based thin film modifier composition,

[0146] The method includes the steps of sequentially injecting a precursor compound and a reaction gas into a chamber to form a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and a vacuum of less than 760 torr, wherein the reaction gas is 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 lowered. This has the effect of minimizing impurity contamination while significantly improving step coverage and uniformity of the thin film thickness, even when forming a thin film on a substrate with a complex structure.

[0147] The step of treating the substrate with the vacuum-based thin film modifier or thin film modifier composition is performed such that the feeding time (seconds [sec]) of the vacuum-based thin film modifier or thin film modifier composition on the substrate surface is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 5 seconds per cycle. Within this range, there are advantages such as a low thin film growth rate, excellent step coverage and economy, as well as minimizing impurity contamination.

[0148] In this description, the feeding time of the precursor compound is based on a flow rate of 0.1 to 500 mg / cycle at a chamber volume of 15 to 20 L, and more specifically, on a flow rate of 0.8 to 200 mg / cycle at 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 aforementioned 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) primary purging the inside of the chamber with a purge gas.

[0151] The thin film modification method, and further the thin film formation method, may, as a preferred embodiment, include: i) vaporizing the vacuum-based thin film modifier or thin film modification composition and treating the surface of a substrate loaded into a chamber; ii) primary purging the inside of the chamber with a purge gas; iii) vaporizing a precursor compound and adsorbing it onto the surface of a substrate loaded into the chamber; iv) secondary purging the inside of the chamber with a purge gas; v) supplying a reaction gas to the inside of the chamber; and vi) tertiary purging the inside 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 of the desired thickness is obtained. In this way, when the vacuum-based thin film modifier or thin film modifier composition of the present invention is added to the substrate before the precursor compound within one cycle and adsorbed onto it, even when deposition is performed at high temperatures, the thin film growth rate can be appropriately reduced, the process by-products generated are effectively removed, the resistivity of the thin film decreases, and the step coverage is greatly 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 temperature conditions of 20 to 800°C.

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

[0155]

[0156] As an example, in the thin film formation method, when the precursor compound is deposited before or after the deposition of the precursor compound, the unit cycle can be repeated 1 to 99,999 times as needed, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film thickness can be obtained while fully achieving the effects to be achieved in the present invention.

[0157]

[0158] The precursor compound is a molecule having one or more ligands consisting of C, N, O, H, X (halogen), and Cp (cyclopentadiene), with 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 a vapor pressure of 1 mTorr to 100 torr at 25°C. In the case of such a precursor, the effect of forming a modified region by the aforementioned vacuum-based thin film modifier or thin film modifier composition can be maximized despite spontaneous oxidation.

[0159] In the present invention, the chamber may, for example, be 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 after vaporization and injection, may be subjected to a plasma post-treatment step, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0162]

[0163] When the vacuum-based thin-film modifier or thin-film modifier composition is first adsorbed onto the substrate, followed by the adsorption of the precursor compound, and then the adsorption of the precursor compound, 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 sufficient to remove the unadsorbed vacuum-based thin-film modifier or thin-film modifier composition. For example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed thin-film modifier or thin-film modifier composition can be sufficiently removed to form a uniform thin film and prevent deterioration of the film quality. Here, the amounts of purge gas, vacuum-based thin-film modifier, and thin-film modifier composition introduced are based on one cycle, and the volume of the vacuum-based thin-film modifier and thin-film modifier composition refers to the volume of vaporized vacuum-based thin-film modifier or thin-film modifier composition vapor.

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

[0165]

[0166] Furthermore, 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 sufficient to remove the unadsorbed precursor compound. For example, it may be 10 to 10,000 times the volume of the precursor compound introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. 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 purge gas and precursor compound introduced are based on one cycle, and the volume of the precursor compound refers to the volume of vaporized precursor compound vapor.

[0167]

[0168] Furthermore, in the purging step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the chamber may, for example, be 10 to 10,000 times the volume of reaction gas introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and within this range, the desired effect can be sufficiently obtained. Here, the amounts of purge gas and reaction gas introduced are based on one cycle each.

[0169]

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

[0171] The substrate loaded into the chamber may be heated to, for example, 100 to 650°C, and more specifically, 150 to 550°C. The vacuum-based thin-film modifier, thin-film modifier composition, or precursor compound may be injected onto the substrate either unheated or heated. Depending on the deposition efficiency, the injection may be performed unheated first, and then the heating conditions may be adjusted during the deposition process. For example, it can be injected onto the substrate at 100 to 650°C for 1 to 20 seconds.

[0172]

[0173] The ratio of the amount (mg / cycle) of the precursor compound to the vacuum-based thin-film modifier or thin-film modifier composition introduced into the chamber is 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 reducing process by-products is significant.

[0174]

[0175] As an example, when the aforementioned thin film formation method uses the vacuum-based thin film modifier or thin film modifying composition and the precursor compound, the reduction rate of the deposition rate represented by the following formula 1 may be 15% or more, specifically 18% or more, preferably 21% or more. In this case, by using the vacuum-based thin film modifier or thin film modifying composition having the aforementioned structure, a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even when applied to substrates with complex structures at high temperatures, the uniformity of the thin film is ensured, the step coverage is greatly improved, and in particular, deposition at a thin thickness is possible. Furthermore, it is possible to improve the amount of O, Si, metals, metal oxides, and even carbon residues that were previously difficult to reduce as process by-products.

[0176] Formula 1

[0177]

number

[0178] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which the thin film is deposited. When a thin film formed by a precursor and reactants is deposited, DR i The initial deposition rate (DR) is the deposition rate of a thin film formed without the addition of a vacuum-based thin film modifier or thin film modifier composition. f The (final deposition rate) is the deposition rate of the thin film formed by introducing a vacuum-based thin film modifier or thin film modifier composition during the process described above. Here, the deposition rate (DR) is measured using an ellipsometer for thin films with a thickness of 3 to 30 nm under normal temperature and pressure conditions, and is measured in Å / cycle units.

[0179] In the above formula 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 refers to the deposited film thickness (Å) of the thin film per cycle, i.e., the deposition rate. As an example, the deposition rate can be determined by measuring the final thin film thickness of a thin film with a thickness of 3 to 30 nm under room temperature and atmospheric pressure conditions using ellipsometry, and then dividing by the total number of cycles to obtain the average deposition rate.

[0180] In the aforementioned formula 1, "when a vacuum-based thin film modifier or thin film modifier composition is not used" means the case in which a thin film is manufactured by adsorbing only the precursor compound onto the substrate during the thin film deposition process. A specific example is the case in which the thin film is formed by omitting the steps of adsorbing the vacuum-based thin film modifier or thin film modifier and purging the unadsorbed vacuum-based thin film modifier or thin film modifier from the thin film formation method.

[0181]

[0182] The aforementioned thin film formation method provides a residual halogen intensity (c / s) within the thin film, measured based on SIMS and based on a film thickness of 100 Å, which is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred embodiment, it may be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and deterioration is outstanding.

[0183] In this description, the purging 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 a single atomic layer (atomic mono-layer) or approximately thereof, which has the advantage of being advantageous in terms of film quality.

[0184]

[0185] The aforementioned ALD (atomic layer deposition process) is highly advantageous for the fabrication of integrated circuits (ICs) that require a high aspect ratio. In particular, its self-limiting thin film growth mechanism offers advantages such as excellent conformality, uniformity, and precise thickness control.

[0186] The aforementioned thin film formation method can, for example, be carried out at an evaporation temperature in the range of 50 to 800°C, preferably in the range of 300 to 700°C, more preferably in the range of 400 to 650°C, even more preferably in the range of 400 to 600°C, and even more preferably in the range of 450 to 600°C. Within this range, it is possible to grow a thin film with excellent film quality while achieving the ALD process characteristics.

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

[0188] In this description, the deposition temperature and deposition pressure may be measured as the temperature and pressure formed within the deposition chamber, or as the temperature and pressure applied to the substrate within the deposition chamber.

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

[0190] Furthermore, the present invention may include a thin film manufacturing apparatus capable of realizing the thin film manufacturing method, comprising: 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 a thin film precursor; and a second transport means for transporting the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the art to which the present invention belongs.

[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, a thin film formation method can be provided, comprising the steps of: treating the surface of a substrate loaded into a chamber with the aforementioned vacuum-based thin film modifier or vacuum-based thin film modification composition; and injecting an etching substance into the chamber to form a vacuum-based etching film on the substrate, wherein the etching substance is one or more selected from Cl2, CCl4, CF2Cl2, CF3Cl, CF4, CHF3, C2F6, SF6, BCl3, Br2, and CF3Br.

[0194] The etching material can be used in combination with Ar, H2, or O2. Aside from this, specific details regarding matters that overlap with the formation of the deposited film are 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 herein. In this case, the step coverage and uniformity of the film thickness of the thin film are significantly superior, and the density and electrical properties of the thin film are also excellent.

[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, and within this range, it has the effect of exhibiting excellent thin film properties.

[0198] The thin film may have a carbon impurity content of preferably 5,000 counts / second [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, the thin film has excellent thin film properties while also having the effect of reducing the thin film growth rate.

[0199] As an example, the aforementioned thin film has a step coverage rate 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 onto a substrate, which has the advantage of being applicable to next-generation semiconductor devices.

[0200] The manufactured thin film preferably has a film thickness of 20 nm or less, a dielectric constant of 5 to 29 relative to a film thickness of 10 nm, a carbon, nitrogen, and halogen content of 5,000 counts / sec or less, and a step coverage ratio of 90% or more. Within this range, it exhibits excellent performance as a dielectric film or blocking film, but is not limited thereto.

[0201]

[0202] The thin film may, as an example, be a multilayer structure of two or three or more layers, preferably a multilayer structure of two or three layers, as needed. The two-layer multilayer film may, as a specific example, be a lower layer-middle layer structure, and the three-layer multilayer film may, as a specific example, be a lower layer-middle layer-upper layer structure.

[0203] The aforementioned underlayer film may, for example, consist of one or more elements 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 aforementioned intermediate layer is, for example, Ti x N y , preferably including TN.

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

[0206] The semiconductor substrate may be a low-resistive metal gate interconnect, a high-aspect-ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA) capacitor, or a 3D NAND flash memory.

[0207]

[0208] The following examples and drawings are provided to aid in understanding the present invention. However, these examples 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 concept. It goes without saying that such modifications and changes also fall within the scope of the attached 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 SiN deposition of Comparative Example 1, a hexachlorodisilane (HCDS) precursor was used, with the canister heating temperature set to 35°C, the N2 carrier gas flow rate set to 40 sccm for 3 seconds, the NH3 flow rate set to 1000 sccm for 30 seconds, and the N2 purge gas flow rate set to 1000 sccm for 12 seconds. This process was repeated 100 to 150 times.

[0214]

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

[0216] Chemical formula 1-1

[0217] [ka]

[0218] During this process, the canister heating temperature was maintained at 50°C, and the N2 carrier gas flow rate was maintained at 100 sccm for 3 seconds. The process of injecting the substance represented by chemical formula 1-1 for 3 seconds was repeated 100 to 150 times.

[0219]

[0220] In Table 1 below, for the SiN experiment in Example 2, the substance 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 injected using a liquid delivery system (LDS) under the conditions of 0.1 g / min for 3 seconds, except that the procedure was repeated in the same manner as the SiN experiment in Example 1.

[0221] Chemical formula 3-1

[0222] [ka]

[0223] The thin films obtained in Comparative Example 1 and Examples 1-2 were analyzed for their 10 nm SiN film thickness by ellipsometry and measured their deposition rate.

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

[0225] *Measurement of deposition rate: The deposition rate per cycle was determined by measuring the film thickness of a SiN thin film deposited to a thickness of 10 nm using ellipsometry optical analysis fitting, and then dividing the obtained film thickness by the total ALD cycle. The reduction rate was calculated using Equation 1 to confirm the reduction rate, and the results are shown in Table 1 below.

[0226] Formula 1

[0227]

number

[0228] [Table 1]

[0229] As shown in Table 1 above, in Example 1, which used the vacuum thin film modifier according to the present invention, it was confirmed that the reduction in deposition rate reached -22% compared to Comparative Example 1, which did not use the vacuum thin film modifier. Furthermore, as shown in Table 1 above, in Example 2, which used the vacuum thin film modifier composition according to the present invention, it was confirmed that the reduction in deposition rate reached a remarkable -30% compared to Comparative Example 1, which did not use the vacuum thin film modifier. Moreover, as shown in Figure 2 below, in Example 2, which used the vacuum thin film modifier composition according to the present invention, as the sputtering time increased, the depth indicated elemental information from the surface to the interior, and as a result of checking the composition of the thin film, it was confirmed that carbon contamination was at a detection limit level of less than 0.1%.

[0230]

[0231] Examples 2-4, Comparative Example 2

[0232] Except for replacing the compound represented by chemical formula 3-1 used in Example 2 with the compounds represented by chemical formulas 3-2, 3-3, and 3-4 below, the same process as in Example 2 was repeated to produce 10 nm SiN thin films. For reference, chemical formula 3-2 corresponds to Example 2, chemical formula 3-3 to Example 3, and chemical formula 3-4 to Comparative Example 2.

[0233] Chemical formula 3-2

[0234] [ka]

[0235] Chemical formula 3-3

[0236] [ka]

[0237] Chemical formula 3-4

[0238] [ka]

[0239] Specifically, for the experiment, the following compounds, each having a dielectric constant of less than 15, were mixed with the compound represented by chemical formula 1-1 in a 1:1 molar ratio: 1:1 with the compound represented by chemical formula 1-1: 1:1 with the compound represented by chemical formula 1-1: 1:1 with the solvent represented by chemical formula 3-1 (d: 1.9 at 25°C), 3-2 (d: 3.7 at 25°C), 3-3 (d: 7.6 at 25°C), and 3-4 (d: 24.5 at 25°C). 1The degree of reactivity was confirmed using 1H-NMR based on the presence or absence of novel impurity peaks, and the results are summarized in Table 2 and Figures 2-5 below. If a novel impurity peak was observed, it was judged to be reactive and indicated with 'O'; if no novel impurity peak was observed, it was judged to be unreactive and indicated with '×'.

[0240] [Table 2]

[0241] As shown in Table 2 and Figures 2-5 below, in Examples 2-4, which incorporated compounds represented by chemical formulas 3-1, 3-2, and 3-3 with dielectric constants of 15 or less, no reactivity with the vacuum thin-film modifier to be used was observed, and it was determined that these compounds are effective in improving the deposition process. On the other hand, in Comparative Example 2, which incorporated a compound represented by chemical formula 3-4 with a dielectric constant greater than 15, reactivity with the vacuum thin-film modifier to be used was observed, and it was determined that these compounds are 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, characterized in that it controls the growth or film quality of a vacuum-based thin film formed from a precursor compound, wherein the aromatic compound having a hydrocarbon group and a halogen group comprises 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 independently selected from hydrogen, a C1-C5 alkyl group, a C1-C5 alkene group, a C1-C5 alkoxy group, and a halogen group, and each contains at least one halogen group.)

2. The vacuum-based thin film modifier according to claim 1, characterized in that the vacuum-based thin film is a vacuum-based deposited film or a vacuum-based etched film.

3. The vacuum-based thin-film modifier according to claim 1, characterized in that in the chemical formula 1, R', R'', and X are hydrogen, an alkyl group having 1 to 5 carbon atoms, and a halogen group, respectively.

4. The vacuum-based thin film modifier according to claim 1, characterized in that the vacuum-based thin film modifier contains a compound represented by the following chemical formulas 1-1 to 1-3. Chemical formula 1-1 【Chemistry 2】 Chemical formula 1-2 【Transformation 3】 Chemical formula 1-3 【Chemistry 4】

5. A vacuum-based thin-film modifier comprising a vacuum-based thin-film modifier according to any one of claims 1 to 4 and an organic solvent having a dielectric constant of 15 or less.

6. The vacuum-based thin-film modification composition according to claim 5, characterized in that the organic solvent having a dielectric constant of 15 or less is a hydrocarbon solvent or a heterocyclic solvent.

7. The vacuum-based thin-film modification composition according to claim 5, characterized in that the organic solvent having a dielectric constant of 15 or less is octane, dimethylethylamine, or tetrahydrofuran.

8. The steps include treating the surface of a substrate loaded into a chamber with a vacuum-based thin-film modifier according to any one of claims 1 to 4, The process involves sequentially injecting a precursor compound and a reaction gas into a chamber to form a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and under a vacuum of less than 760 torr. Includes, A method for forming a thin film, characterized in that the reaction gas is an oxidizing agent or a reducing agent.

9. The step of treating the surface of a substrate loaded into a chamber with the vacuum-based thin film modification composition described in Claim 5, The process involves sequentially injecting a precursor compound and a reaction gas into a chamber to form a vacuum-based deposited thin film on the substrate at a temperature of 20 to 800°C and under a vacuum of less than 760 torr. Includes, A method for forming a thin film, characterized in that the reaction gas is an oxidizing agent or a reducing agent.

10. The thin film formation method according to claim 8, characterized in that the chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

11. The thin film formation method according to claim 9, characterized in that the chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

12. The thin film formation method according to claim 8, characterized in that the vacuum-based thin film modifier and precursor compound are transported into the chamber by a VFC (Vapor Flow Control) system, a DLI (Direct Liquid Injection) system, or an LDS (Liquid Delivery System) system, and the heating temperature of the injection line is 25 to 200°C on the substrate.

13. The thin film formation method according to claim 9, characterized in that the vacuum-based thin film modification composition and precursor compound are transported into the chamber by a VFC (Vapor Flow Control) system, a DLI (Direct Liquid Injection) system, or an LDS (Liquid Delivery System) system, and the heating temperature of the injection line is 25 to 200°C on the substrate.

Images