Dielectric film activator, semiconductor substrate and semiconductor device manufactured using the same

Abstract

The present invention relates to a dielectric film activator, and a semiconductor substrate and a semiconductor device manufactured using the same. According to the present invention, by using a dielectric film activator that can reduce the amount of carbon compounds by-produced by a precursor and a reaction gas mixed into a dielectric film and provide an effect of increasing the density of the thin film, the capacitance of the dielectric film can be improved and an effect of increasing the density of the thin film can be provided through a simple process.

Description

[Technical Field]

[0001] The present invention relates to a dielectric film activator, and a semiconductor substrate and a semiconductor device manufactured using the same. More particularly, the present invention relates to a dielectric film activator that can reduce residual carbon compound impurities of precursors and reaction gases mixed into a dielectric film, thereby improving capacitance and increasing thin film density, and a semiconductor substrate and a semiconductor device manufactured using the same. [Background technology]

[0002] A dielectric is an insulator that does not allow electricity to flow but takes on a polarity in an electric field, and dielectrics play a very important role in semiconductor elements.

[0003] As an example, in a capacitor, the material in which the electricity is actually stored is the dielectric.

[0004] On the other hand, when a high dielectric constant (high-k) material is contaminated with carbon compounds by-produced from the precursor and reaction gases, it can cause a very large capacitance difference.

[0005] The content of residual carbon compound impurities, including impurities of precursors and reactant gases, mixed into the dielectric film is a factor that affects the dielectric properties and chemical properties, and may reduce the dielectric constant. Alternatively, by-products such as HCl and hydrocarbons derived from the leaving groups of halogen ligands may be absorbed and contaminate the dielectric film or disturb the crystal arrangement of the dielectric film, resulting in a decrease in the film density and a decrease in the dielectric constant.

[0006] For this reason, there is a demand for the development of a dielectric film activator that can reduce the content of residual carbon compound impurities, including impurities of precursors and reactant gases, mixed into the dielectric, while increasing the density of the thin film and thereby increasing the dielectric constant, as well as the manufacture of a dielectric film using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom.

[0007] [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent Publication No. 2020 / 0316645 (Publication Date: October 8, 2020) Summary of the Invention [Problem to be solved by the invention]

[0009] In order to solve the above-mentioned problems of the conventional techniques, the present invention aims to provide a high-quality dielectric film having increased capacitance and film density by activating a precursor adsorbed on a substrate using a dielectric film activator having a predetermined structure and preventing the inclusion of carbon compounds by-produced from the precursor and reaction gas in the dielectric film, as well as a semiconductor substrate and a semiconductor device including the same.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0011] To achieve the above object, the present invention provides a dielectric film activator that converts a first ligand directly bonded to the central metal of a precursor adsorbed on a substrate into a second ligand contained in the dielectric film activator, thereby providing an activated substrate-adsorbed precursor.

[0012] The central metal of the precursor may be, for example, a Group 4 element.

[0013] The central metal of the precursor may be, for example, Hf or Zr.

[0014] The precursor molecules adsorbed on the substrate may be at least one selected from the structure represented by Chemical Formula 1 below and the structure represented by Chemical Formula 2 below.

[0015] [Chemical formula 1]

[0016] [ka]

[0017] (In the above chemical formula 1, M is Zr or Hf, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, X'1, X'2, and X'3 are independently selected from -NR'1R'2 or -OR'3, Cl, or F, and R'1 to R'3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms.)

[0018] [Chemical formula 2]

[0019] [ka]

[0020] (In the above chemical formula 2, M is Zr or Hf, X1 and X2 are independently —NR1R2 or —OR3, Cl, or F, R1 to R3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, Y is an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.)

[0021] The precursor molecule adsorbed on the substrate may have a structure in which four types of ligands independently selected from -NR'1R'2 or -OR'3, Cl, or F are bound to a central metal. Here, the central metal may be Zr or Hf, and R'1 to R'3 may independently be hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0022] The first and second ligands may, independently of one another, contain a halogen, a halogen and oxygen, or carbon and hydrogen at the same time, or nitrogen and carbon at the same time.

[0023] The first ligand is the ligand of Formula 1 or Formula 2 above, and the ligand of the precursor adsorbed on the substrate may additionally include one or more selected from chlorine, fluorine, and bromine, and the dielectric film activator may include one or more halogens selected from iodine and bromine.

[0024] The dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas obtained by mixing these with an inert gas at a molar fraction of 1 to 99.

[0025]

[0026] The activated substrate-adsorbed precursor promotes reaction with a pre-injected or post-injected reactant gas prior to the precursor, and the content of residual carbon compound impurities is reduced.

[0027] The reduction in the content of residual carbon compound impurities may include a reduction in the content of by-product carbon-oxygenate impurities generated by binding of precursor desorbed ligands with reactants, and a reduction in the content of carbon compound impurities that are not desorbed from the precursor.

[0028] The decrease in the content of the undesorbed carbon compound impurities may be due to the replacement of the ligands of the precursor adsorbed on the substrate with the dielectric film activator contained in the dielectric film activator.

[0029] The reactive gas may be at least one selected from the group consisting of H2O, H2O2, N2O, NO2, O2, O3, and O radicals.

[0030]

[0031] The adsorption state of the precursor before the ligand exchange can be represented by the following chemical formula 3-1, and the adsorption state of the precursor after the ligand exchange can be represented by the following chemical formula 3-2.

[0032] [Chemical formula 3-1]

[0033] [ka]

[0034] (In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, and X is a ligand species of Chemical Formula 1, Chemical Formula 2, F, or Cl, and may be different from each other.)

[0035] [Chemical formula 3-2]

[0036] [ka]

[0037] (In the above chemical formula 3-2, M is Hf or Zr, M is an integer of 1 to 4, and Y is Br or I.)

[0038]

[0039] The substrate can be a silicon wafer, an insulating film, or a dielectric film having -H or -OH terminal groups.

[0040] The dielectric film may be a vapor-deposited film.

[0041] Here, the deposition can be atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), vapor deposition (CVD), plasma-enhanced vapor deposition (PECVD), metalorganic chemical vapor deposition (MOCVD), or low-pressure vapor deposition (LPCVD).

[0042]

[0043] The present invention also provides a method for manufacturing a semiconductor device comprising:

[0044] The semiconductor substrate is characterized in that the dielectric film is a film deposited using the dielectric film activator described above.

[0045] The dielectric film may have a multi-layer structure of two or more layers.

[0046] The dielectric film may have a deposition rate measured on SiO2 or Si (based on a thin film deposited at 300°C) of 0.5 Å / cycle or greater.

[0047] ( The dielectric film has a thin film density of 9.8 g / cm measured on SiO2 or Si. 3 It could be more than that.

[0048] The dielectric film may have a C impurity content of 1000 counts / s or less as measured by SIMS (based on a thin film deposited at 300° C.) on SiO 2 or Si.

[0049] The present invention further provides a semiconductor device including the semiconductor substrate described above. [Effects of the Invention]

[0050] According to the present invention, the activated substrate adsorbed precursor promotes reaction with a post-injected reaction gas, and the present invention has the effect of providing a dielectric film activator capable of reducing the content of residual carbon compound impurities.

[0051] Specifically, the density is improved during the formation of the dielectric film, and the process by-products are more effectively reduced, preventing corrosion and deterioration, and improving the dielectric properties of the dielectric film.

[0052] Furthermore, the thickness uniformity of the dielectric film can be improved, and further, a method for manufacturing a dielectric film using the same, and a semiconductor substrate and a semiconductor device manufactured using the same can be provided. [Brief explanation of the drawings]

[0053] [Figure 1] FIG. 1 is a graph comparing the growth rate of the dielectric film of Example 1, in which a dielectric film activator was used according to the present invention, at each deposition temperature, with the growth rate of the dielectric film of Comparative Example 1, in which a dielectric film activator was not used, at each deposition temperature.

[0054] [Figure 2] 1 is a graph showing the content of C impurities by SIMS analysis in the dielectric film of Additional Example 1 in which a dielectric film activator was used according to the present invention.

[0055] [Figure 3] 10 is a graph showing the content of C impurities by SIMS analysis in the dielectric film of Additional Comparative Example 1, in which no dielectric film activator was used.

[0056] DETAILED DESCRIPTION OF THE INVENTION

[0057] The dielectric film activator described above, and the semiconductor substrate and semiconductor device manufactured using the same will be described in detail below.

[0058]

[0059] The present inventors have found that when a dielectric film is formed using a dielectric film activator that can provide an effect of increasing thin film density while reducing the content of by-product carbon-oxygen impurities generated by the bonding of precursor desorbed ligands and reactants mixed into the dielectric film and the content of carbon compound impurities not desorbed from the precursor, density is improved, corrosion and deterioration are prevented, and the dielectric properties of the dielectric film are improved, and the thickness uniformity of the dielectric film is improved, thereby providing a high-quality dielectric film. Based on this finding, the present inventors have incorporated this finding into their research on dielectric films and have completed the present invention.

[0060]

[0061] Hereinafter, the dielectric film activator, and the semiconductor substrate and semiconductor device including the dielectric film manufactured using the same will be described in detail.

[0062]

[0063] In this description, the dielectric film activator may be a substance that activates a precursor adsorbed on a substrate in the present invention, thereby promoting the reaction of the activated substrate-adsorbed precursor with a post-injected reaction gas, and also reducing the inclusion of residual carbon compound impurities in the dielectric film.

[0064] The central metal of the precursor adsorbed on the substrate may be a Group 4 element, and the ligands may contain two or more halogens that may be the same or different and be adsorbed on the substrate.

[0065] The central metal may preferably be Hf or Zr.

[0066] The precursor compounds used in the present invention to form the dielectric film are composed of Group 4 metals, Hf and Zr, and may be Hf(NMe2)4, Zr(NMe2)4, CpZr (CpZr(NMe2)3), CpHf (CpHf(NMe2)3), and derivatives thereof with Hf or Zr as the central metal, and may be linear or cyclic precursor molecules linked with ligands bonded to the central metal.

[0067]

[0068] The precursor molecules adsorbed on the substrate can be represented by, for example, the following Chemical Formula 1 and Chemical Formula 2:

[0069] [Chemical formula 1]

[0070] [ka]

[0071] (In the above chemical formula 1, M is Zr or Hf, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, X'1, X'2, and X'3 are independently selected from -NR'1R'2 or -OR'3, Cl, or F, and R'1 to R'3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms.)

[0072] [Chemical formula 2]

[0073] [ka]

[0074] (In the above chemical formula 2, M is Zr or Hf, X1 and X2 are independently —NR1R2 or —OR3, Cl, or F, R1 to R3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, Y is an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.)

[0075] In the case of a precursor having a transition metal as a central metal atom (M) and one or more ligands consisting of C, N, O, H, and X (halogen), and having a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of substituting the ligand with a dielectric film activator described below can be maximized.

[0076]

[0077] Examples of zirconium precursor compounds that can be used include tris(dimethylamido)cyclopentadienylzirconium (CpZr(NMe2)3), (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)zirconium (Cp(CH2)3NM3Zr(NMe2)2), and tetrakis(ethylmethylamido)zirconium ([(Me)(Et)N]4Zr). In these cases, the dielectric film activator described below can be used to appropriately fill the compounds.

[0078] Examples of hafnium precursor compounds that can be used include tris(dimethylamido)cyclopentadienylhafnium (CpHf(NMe2)3), (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium (Cp(CH2)3NM3Hf(NMe2)2), and tetrakis(ethylmethylamido)hafnium ([(Me)(Et)N]4Hf), which can be appropriately filled with the dielectric film activator described above.

[0079] In the present invention, the precursor compound may be mixed with a non-polar solvent and then introduced into the chamber, which has the advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0080] The non-polar solvent may be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, the non-polar solvent contains an organic solvent that has low reactivity and solubility and allows easy moisture control, and the thin film density (step coverage) is improved even when the deposition temperature is elevated during the formation of the dielectric film. This has the advantage that:

[0081] In a more preferred example, the non-polar solvent is a C1 to C 10 Alkanes of C3 to C 10 The cycloalkanes may include cycloalkanes of the formula C3 to C6. 10 In this case, the advantage is that the reactivity and solubility are low, and moisture can be easily controlled.

[0082] In this description, C1, C3, etc. refer to the number of carbon atoms.

[0083] The cycloalkane is preferably a C3 to C 10 Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, so it is suitable for the vapor deposition process, but is not limited thereto.

[0084] The non-polar solvent has, for example, a solubility in water (at 25°C) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantage of low reactivity with the precursor compound and easy water management.

[0085] In this description, the solubility is not particularly limited to the measurement methods and standards commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by high performance liquid chromatography (HPLC).

[0086] The non-polar solvent preferably comprises 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0087] If the content of the non-polar solvent exceeds the upper limit, it may cause impurities, increasing the resistance and the number of impurities in the dielectric film. If the content of the organic solvent is less than the lower limit, the effect of adding the solvent to improve the film density and reduce impurities such as chlorine (Cl) ions may not be obtained.

[0088]

[0089] The first and second ligands may, independently of one another, contain a halogen, a halogen and oxygen, or carbon and hydrogen simultaneously, or may contain nitrogen and carbon simultaneously.

[0090] The first ligand is the ligand of Formula 1 or Formula 2 above, and the ligand of the precursor adsorbed on the substrate may additionally include one or more selected from chlorine, fluorine, and bromine, and the dielectric film activator may include one or more halogens selected from iodine and bromine.

[0091] The dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas obtained by mixing these with an inert gas at a molar fraction of 1 to 99.

[0092]

[0093] A substance having a structure in which the above-mentioned ligand is bound to these central metals can be used as a precursor adsorbed on a substrate, and here, by activating it with the above-mentioned dielectric film activator, a precursor adsorbed on an activated substrate can be obtained.

[0094] The activated substrate-adsorbed precursor promotes reaction with the post-injected reaction gas and reduces the content of residual carbon compound impurities.

[0095] Here, the reduction in the content of residual carbon compound impurities may include a reduction in the content of by-product carbon-oxygen impurities generated by binding of the precursor desorbed ligand with the reactant, and a reduction in the content of carbon compound impurities that are not desorbed from the precursor.

[0096] Specifically, the decrease in the content of the undesorbed carbon compound impurities may be due to the replacement of the ligands of the precursor adsorbed on the substrate with the dielectric film activator contained in the dielectric film activator.

[0097]

[0098] The adsorption state of the precursor before the ligand exchange can be represented by the following chemical formula 3-1, and the adsorption state of the precursor after the ligand exchange can be represented by the following chemical formula 3-2.

[0099] [Chemical formula 3-1]

[0100] [ka]

[0101] (In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, and X is a ligand species of Chemical Formula 1, Chemical Formula 2, F, or Cl, and may be different from each other.)

[0102] [Chemical formula 3-2]

[0103] [ka]

[0104] (In the above chemical formula 3-2, M is Hf or Zr, M is an integer of 1 to 4, and Y is Br or I.)

[0105] For example, when the precursor adsorbed on the substrate is CpHf(NMe2)3, the precursor structure adsorbed on the substrate activated by the dielectric film activator is represented by the above formula 3-1 (substrate-MX n ), M is Hf, and X, which may be different from each other, may be one Cp ligand and two NMe2 ligands.

[0106]

[0107] The substrate can be a silicon wafer, an insulating film, or a dielectric film having -H or -OH terminal groups.

[0108] The ligand of the precursor adsorbed on the substrate may be, for example, a ligand species having the structure represented by Formula 1 or 2 above, or may be F or C.

[0109] The ligands of the precursor adsorbed on the substrate may be, as another example, independently selected from -NR'1R'2 or -OR'3, Cl, or F, where R'1 to R'3 may independently be hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0110]

[0111] When the precursor adsorbed on the substrate contains one or more halogens selected from chlorine, fluorine, nitrogen compounds, and carbon compounds, it is preferable that the dielectric film activator be a nitrogen compound or a carbon compound, rather than chlorine or fluorine, which reacts with the iodine-based and bromine-based activators.

[0112] As a specific example, the dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas obtained by mixing these with an inert gas at a molar fraction of 1 to 99.

[0113] The dielectric film activator may be an iodine donor, an iodine ion, or an iodine radical, and is preferably a substance represented by the above structure in terms of smooth ligand exchange.

[0114] In this case, side reactions are suppressed, process by-products in the dielectric film are reduced, corrosion and deterioration are reduced, the growth rate of the thin film is controlled, and a stoichiometric oxidation state is reached during the formation of the metal oxide film, resulting in a significant improvement in the thickness uniformity of the dielectric film.

[0115] Specifically, the dielectric film activator may be 3N to 15N hydrogen iodide alone, a gas mixture of 1 to 99% by weight of 3N to 15N hydrogen iodide and the balance of an inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 3N to 15N hydrogen iodide and the balance of water to make the total amount 100% by weight. Here, when the inert gas is nitrogen, helium, or argon with a purity of 4N to 9N, it is possible to significantly reduce process by-products and achieve excellent thin film density, as well as to further improve the thin film density and electrical properties.

[0116] Preferably, the dielectric film activator is 5N to 6N hydrogen iodide alone, a gas mixture of 5N to 6N hydrogen iodide at 1 to 99% by weight with an inert gas balance to make the total amount 100% by weight, or an aqueous solution mixture of 5N to 6N hydrogen iodide at 0.5 to 70% by weight with water balance to make the total amount 100% by weight, where the inert gas may be nitrogen, helium, or argon with a purity of 4N to 9N. In this case, side reactions are suppressed, the growth rate of the thin film is adjusted, process by-products in the thin film are reduced, corrosion and degradation are reduced, the crystallinity of the thin film is improved, and the step coverage and thickness uniformity of the thin film are significantly improved even when the thin film is formed on a substrate with a complex structure.

[0117]

[0118] The dielectric film activator 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, if a compound with a purity of less than 99% is used, impurities may remain in the dielectric film or may cause side reactions with the precursor or reactant, so it is best to use a substance with a purity of 99% or more as much as possible.

[0119] The vapor pressure can be 1 atmosphere at 180-240K, and within this range, the material is smoothly transferred into the chamber, resulting in excellent effects of improving the uniformity of the dielectric film thickness, dielectric properties, and film quality.

[0120] In the present invention, the dielectric film activator may be injected in a gaseous state, and the precursor compound described below may be vaporized and injected, followed by a plasma post-treatment. In this case, the growth rate of the dielectric film may be improved while reducing process by-products.

[0121]

[0122] The thin film (including the dielectric film) may be a vapor-deposited film.

[0123] The deposition can be atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), vapor deposition (CVD), plasma-enhanced vapor deposition (PECVD), metal-organic chemical vapor deposition (MOCVD), or low-pressure vapor deposition (LPCVD).

[0124]

[0125] The reactive gas may be at least one selected from the group consisting of H2O, H2O2, N2O, NO2, O2, O3, and O radicals.

[0126]

[0127] The dielectric film can be manufactured by a variety of methods, and for example, it can be manufactured by the following method:

[0128] In the first step, a precursor compound having a transition metal ligand containing alkyl, alkylamine, or halogen, halogen and oxygen, or carbon and hydrogen simultaneously, or nitrogen and carbon simultaneously, can be injected onto a substrate placed in a chamber.

[0129] The ligand may be one or more selected from alkyl, alkylamine, chlorine, and fluorine, and preferably contains alkylamine, which has excellent reactivity.

[0130] The structure containing both carbon and hydrogen may be, for example, a cyclopentadienyl (Cp) group.

[0131] In this description, examples of methods that can be used to distribute the precursor compound throughout the deposition chamber include a method of transporting a vaporized gas using a gas phase mass flow controller (MFC) (Vapor Flow Control; VFC, vapor flow control), a mass flow controller method (MFC) including a liquid phase mass flow controller (LMFC), and a method of transporting a liquid (Liquid Delivery System; LDS, liquid supply system).

[0132] In this case, the carrier gas or dilution gas for transporting the precursor compound onto the substrate may be one or a mixture of two or more gases selected from the group consisting of argon (Ar), nitrogen (N), and helium (He), but the present invention is not limited thereto.

[0133] In this description, the purge gas may be, for example, an inert gas, and preferably the carrier gas or dilution gas.

[0134] The chamber can be an atomic layer deposition (ALD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, a vapor deposition (CVD) chamber, a plasma-enhanced vapor deposition (PECVD) chamber, a metalorganic chemical vapor deposition (MOCVD) chamber, or a low-pressure vapor deposition (LPCVD) chamber.

[0135] The substrate loaded into the chamber may include a semiconductor substrate such as a silicon substrate or silicon oxide substrate.

[0136] The substrate may further have a conductive layer or an insulating layer formed thereon.

[0137] The substrate can be maintained at a temperature of 50 to 500°C, or 80 to 500°C.

[0138] The substrate may be heated to, for example, 50 to 500°C, specifically, 80 to 500°C, 100 to 800°C, or 200 to 500°C. The dielectric film activator or precursor compound may be injected onto the substrate in an unheated or heated state. Depending on the deposition efficiency, the heating conditions may be adjusted during the deposition process after injection in an unheated state. For example, the dielectric film activator or precursor compound may be injected onto the substrate at a temperature of 50 to 500°C for 1 to 20 seconds.

[0139] The amount (mg / cycle) of the precursor compound introduced into the chamber is, for example, 1:1 to 1:100, preferably 1:1 to 1:50, and more preferably 1:1 to 1:25, in terms of the ratio of the amount (mg / cycle) of the dielectric film activator used in the second step described below to the amount (mg / cycle) of the precursor compound introduced into the chamber. Within this range, the effect of improving the thin film density and the effect of reducing process by-products are outstanding.

[0140]

[0141] The first step may include one or more purging steps with an inert gas, which may be the carrier gas or diluent gas described above.

[0142] The amount of purge gas introduced into the chamber in the step of purging the unadsorbed precursor compound is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor compound, but for example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the precursor compound introduced into the chamber. Within this range, the unadsorbed precursor compound can be sufficiently removed to form a uniform dielectric film and prevent deterioration of film quality. Here, the amounts of purge gas and precursor compound introduced are each based on one cycle, and the volume of the precursor compound refers to the volume of vaporized precursor compound vapor.

[0143] In this description, the purge flow 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 close to an atomic monolayer, which is advantageous in terms of film quality.

[0144]

[0145] In the second step, a dielectric film activator is injected into the substrate to exchange the leaving groups of the precursor adsorbed on the substrate with the halogen of the activator. In this case, the leaving groups of the precursor adsorbed on the substrate are effectively converted to the halogen of the activator, thereby forming a thin film without gaps in the crystal lattice, thereby improving the thin film density and significantly improving the dielectric properties and thickness uniformity of the thin film.

[0146] The halogen may be, for example, one or more selected from iodine and bromine, and it is preferable to use iodine.

[0147] The feeding time (seconds) of the dielectric film activator to the surface of the substrate is preferably 0.01 to 10 seconds per cycle, more preferably 0.02 to 3 seconds, even more preferably 0.04 to 2 seconds, and most preferably 0.05 to 1 second. Within this range, there are advantages such as a low thin film growth rate, excellent thin film density, and high economic efficiency.

[0148] In this description, the supply amount of the dielectric film activator is based on a flow rate of 1 to 300 sccm / cycle in a chamber volume of 15 to 20 L, more specifically, based on a flow rate of 10 to 100 sccm / cycle in a chamber volume of 18 L.

[0149] In this description, as a method for spreading the dielectric film activator throughout the deposition chamber, for example, a method for transporting a gas using a gas phase mass flow controller (MFC) method can be used.

[0150] The second step may include one or more purging steps using an inert gas, which may be, for example, the carrier gas or diluent gas.

[0151] In this description, the purge flow 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 an atomic monolayer or so close to it, which is advantageous in terms of film quality.

[0152] The amount of purge gas introduced into the chamber in the step of purging the unadsorbed dielectric film activator is not particularly limited as long as it is an amount sufficient to remove the unadsorbed dielectric film activator, but may be, for example, 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed dielectric film activator can be sufficiently removed to form a uniform thin film and prevent deterioration of film quality. Here, the amounts of purge gas and dielectric film activator introduced are each based on one cycle, and the volume of the dielectric film activator refers to the volume of evaporated dielectric film activator vapor.

[0153]

[0154] As a specific example, in the step of injecting (per cycle) the deposition filler at a flow rate of 100 sccm and for an injection time of 0.5 seconds, and purging unadsorbed deposition filler, if a purge gas is injected (per cycle) at a flow rate of 3000 sccm and for an injection time of 5 seconds, the injection amount of the purge gas is 300 times the injection amount of the deposition filler.

[0155]

[0156] Then, in the third step, a reactive gas may be injected onto the substrate to form a thin film in which heteroatoms are bonded to the transition metal.

[0157] The reactive gas may be, for example, one or more selected from H2O, H2O2, N2O, NO2, O2, O3, and O radicals.

[0158] The thin film may include a structure in which a halogen is directly bonded to a Group 4 metal.

[0159] The method for forming the dielectric film may be carried out at a deposition temperature in the range of, for example, 50 to 800°C, preferably 100 to 700°C, more preferably 200 to 650°C, and even more preferably 220 to 500°C. Within this range, it is possible to achieve process characteristics while growing a thin film with excellent film quality.

[0160] The method for forming the dielectric film can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, a thin film with a uniform thickness can be obtained.

[0161] In this description, the deposition temperature and deposition pressure may be measured as the temperature and pressure formed in the deposition chamber, or may be measured as the temperature and pressure applied to the substrate in the deposition chamber.

[0162] The second step may preferably further include a step of raising the temperature in the chamber to a deposition temperature before introducing the dielectric film activator into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the dielectric film activator into the chamber.

[0163] The third step may include a purging step with an inert gas.

[0164] 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, and 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.

[0165] In this description, the purge flow 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 close to an atomic monolayer, which is advantageous in terms of film quality.

[0166]

[0167] The method for forming the dielectric film can be carried out by repeating the unit cycle 1 to 99,999 times as necessary, 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 content of by-produced carbon compounds can be reduced and the density of the thin film can be improved while obtaining the desired thin film thickness.

[0168]

[0169] In a specific example of the method for manufacturing the dielectric film, the above-described dielectric film activator and a precursor compound or a mixture thereof with a non-polar solvent are prepared to deposit a dielectric film on a substrate placed in the deposition chamber.

[0170] Then, the precursor compound or a mixture thereof with a non-polar solvent is injected into an evaporator, converted into a vapor phase, and spread throughout the deposition chamber to be adsorbed onto the substrate. The ligands of the precursor compound are replaced by a dielectric film activator, while the unadsorbed precursor compound is purged.

[0171] Next, the prepared dielectric film activator is injected into an evaporator, converted into a vapor phase, and spread throughout the deposition chamber to be adsorbed onto the substrate, followed by purging to remove any unadsorbed dielectric film activator.

[0172] In this description, as a method for distributing the dielectric film activator and precursor compounds in the deposition chamber, for example, a method for transporting gases using a gas phase mass flow controller (MFC) method can be used.

[0173] In this case, the carrier gas or dilution gas for transporting the dielectric film activator and precursor compound onto the substrate may be one or a mixture of two or more gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0174] In this description, the purge gas may be, for example, an inert gas, and preferably the carrier gas or dilution gas.

[0175] Next, a heteroatom-containing gas is supplied. The heteroatom-containing gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and preferably includes an oxidizing agent. The oxidizing agent reacts with the precursor compound adsorbed on the substrate to form an oxide film.

[0176] Preferably, the oxidizing agent may be oxygen gas (O2), ozone gas (O3), or a mixture of nitrogen gas and oxygen gas.

[0177] Next, purge the unreacted residual reactants using an inert gas. This can remove not only the excess reactants but also the generated by-products together.

[0178] As described above, as an example, the method for forming the dielectric film includes steps of adsorbing a precursor compound onto a substrate, purging the unadsorbed precursor compound, supplying a dielectric film activator onto the substrate, purging the unadsorbed dielectric film activator, supplying a reaction gas, and purging the residual reaction gas, which are used as a unit cycle. To form a dielectric film with a desired film thickness, the unit cycle can be repeated.

[0179] As an example, the unit cycle can be repeated 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, there is an effect that the characteristics of the target dielectric film can be well expressed.

[0180]

[0181] When the injection time and purge time of the precursor compound in the first and second steps are a and b respectively, the injection time and purge time of the alkyl-free halide in the second step are c and d respectively, and the injection time and purge time of the heteroatom-containing gas in the third step are e and f respectively, 0.1 ≦ a ≦ 10, 2a ≦ b ≦ 4a, 0.1 < c ≦ 10, 2c ≦ d ≦ 8c, 2 < e ≦ 10, and 2e ≦ b ≦ 8e can be simultaneously satisfied. [[ID=##]]

[0182] [[ID=##]] [[ID=##]] [[ID=##]]<00,00630>[[ID=##]] When the injection and purge of the precursor compound and the dielectric film activator, and the injection and purge of the heteroatom-containing gas are regarded as one cycle, the following two conditions are met: 1) the deposition rate of the dielectric film on SiO2 is 1 Å / cycle or more, and 2) the density of the dielectric film is 9.8 g / cm 3Both of the above may be satisfied.

[0184] When the injection and purging of the precursor compound and the dielectric film activator, and the injection and purging of the heteroatom-containing gas constitute one cycle, the deposition was carried out under the following two conditions: 1) the deposition rate of the dielectric film on SiO2 is 1 to 2 Å / cycle, and 2) the density of the dielectric film is 9.8 to 10.5 g / cm. 3 Both of these can be satisfied.

[0185] For example, the dielectric film manufacturing method may be performed using a dielectric film manufacturing apparatus including an ALD chamber, a corrosion-resistant mass flow controller (MFC) including a gold seal for supplying a fixed amount of a dielectric film activator, a first transport means for transporting the supplied dielectric film activator into the ALD chamber, a second evaporator for vaporizing the precursor adsorbed on the substrate, and a second transport means for transporting the vaporized precursor adsorbed on the substrate into the ALD chamber. Here, the evaporator and transport means are not particularly limited as long as they are evaporators and transport means commonly used in the technical field to which the present invention pertains.

[0186]

[0187] The dielectric film includes a thin film deposited using the aforementioned activator.

[0188] The thin film may be a dielectric film.

[0189] The thin film may have a multi-layer structure of two or more layers.

[0190] For example, the thin film may be obtained by reacting an activated substrate-adsorbed precursor represented by the structure of Chemical Formula 1 with a reactive gas. In this case, the use of the activated substrate-adsorbed precursor can reduce the content of by-product carbon compounds, allowing the production of a high-quality thin film.

[0191] The reduction in the by-product carbon compounds of the precursor adsorbed on the activated substrate and the reaction gas may be due, for example, to the activation energy of the precursor adsorbed on the activated substrate being lower than the activation energy of the precursor adsorbed on the substrate.

[0192]

[0193] The deposition rate of the dielectric film on SiO2 or Si, as measured by an ellipsometer (based on a thin film deposited at 300°C), may be 1.0 Å / cycle or more, or 1.0 to 2.0 Å / cycle, and within this range, thin film uniformity and deposition productivity can be improved.

[0194] The dielectric film has a thin film density of 9.5 g / cm measured on SiO2 or Si. 3 More than 9.8g / cm 3 or more, or 9.8 to 10.3 g / cm 3 Within this range, the dielectric properties can be improved.

[0195] The dielectric film may have a carbon impurity content of 1000 counts / s or less, 715 counts / s or less, or 700 counts / s or less as measured by SIMS (based on a thin film deposited at 300°C) on SiO2 or Si, and within this range, electron leakage is significantly reduced, thereby improving the dielectric properties.

[0196] The dielectric film may have an iodine atom density of 50 counts / s or more, or 65 counts / s or more, as measured by SIMS, and within this range, the film density can be increased, resulting in a high dielectric constant.

[0197] The dielectric film may have a deposition thickness of 410 counts / s or less, or 300 counts / s or less, measured by SIMS (based on a thin film deposited at 400°C) on SiO2 or Si, and within this range, electron leakage is significantly reduced, thereby improving the dielectric properties.

[0198] The dielectric film may contain the above-mentioned film composition alone or in a selective area, but the present invention is not limited thereto and is meant to encompass Si, SiH, SiOH, and SiO2.

[0199] The dielectric film can be used in semiconductor devices as a dielectric film or insulating film for not only commonly used DRAM but also NAND or logic devices.

[0200] For example, the dielectric film may contain halogen compounds at 30,000 counts / s or less as measured using SIMS.

[0201]

[0202] The present invention also provides a semiconductor substrate, which is manufactured by the above-described method for forming a dielectric film or includes the above-described dielectric film. In such cases, the dielectric film has significantly superior step coverage and thickness uniformity, and also has excellent density and dielectric properties.

[0203]

[0204] The dielectric film thus produced preferably has a deposition rate on SiO2 of 1 Å / cycle or more and a density of 9.8 g / cm 3 Within the above range, the performance as a diffusion barrier film is excellent, and in particular, the dielectric properties are improved, but the present invention is not limited to this range.

[0205] Here, the impurity halogen remaining in the dielectric film may be, for example, Cl, Cl, or Cl. - The lower the amount of residual halogen in the dielectric film, the better the film quality, which is preferable.

[0206] Furthermore, the lower the content of carbon remaining in the dielectric film, the better the dielectric properties will be, which is preferable.

[0207]

[0208] The dielectric film may have a multilayer structure of two or more layers, a multilayer structure of three or more layers, or a multilayer structure of two or three layers, as required. A multilayer film having a two-layer structure may have a lower layer film-middle layer film structure, and a multilayer film having a three-layer structure may have a lower layer film-middle layer film-upper layer film structure.

[0209] The underlayer film may, for example, contain 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.

[0210] The intermediate layer film may be, for example, Ti x N y , preferably TN.

[0211] The upper layer film may contain, for example, one or more selected from the group consisting of W and Mo.

[0212]

[0213] According to the present invention, a semiconductor device including the semiconductor substrate described above can be provided.

[0214] The semiconductor device may be, for example, a low-resistive metal gate interconnect structure, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA), or a 3D NAND flash memory.

[0215]

[0216] Below, preferred examples and drawings are presented to help understand the present invention better. However, the following 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 idea thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0217]

[0218] [Example]

[0219] As precursor compounds, a compound having a structure represented by the following chemical formula 1-1 and a compound having a structure represented by the following chemical formula 4 were prepared.

[0220] [Chemical Formula 1-1] (Cyclopentadienyl Ligand Precursor)

[0221] [ka]

[0222] [Chemical Formula 4] (Alkylamine Ligand Precursor)

[0223] [ka]

[0224] As a dielectric film activator, 5N HI was prepared.

[0225] Using the precursor compound and the dielectric film activator, an ALD process was carried out with the deposition process sequence according to the present invention as one cycle.

[0226]

[0227] The specific experimental methods for Examples 1 and 2 and Comparative Examples 1 and 2 are as follows.

[0228] Example 1

[0229] The precursor compound represented by Formula 1-1 was placed in a canister maintained at 25°C and supplied to a separate evaporator heated to 150°C at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. The precursor compound vaporized in the evaporator was introduced into a deposition chamber using a vapor mass flow controller (VFC) for 1 second, and then argon gas was supplied at 3000 sccm for 5 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0230] Next, 5N HI was placed in a canister as a dielectric film activator and supplied to the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature. After the dielectric film activator was introduced into the deposition chamber containing the substrate for 2 seconds, argon gas was supplied at 3000 sccm for 8 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0231] Next, 1000 sccm of ozone as a reactive gas was introduced into the reaction chamber for 3 seconds, and then argon purging was performed for 9 seconds. At this time, the substrate on which the dielectric film was to be formed was heated to 300°C, and the substrate was a Si substrate with SiO2 formed on top.

[0232] This process was repeated 200 to 400 times to produce a dielectric film at a deposition rate according to the deposition temperature as shown in FIG. 1 below.

[0233] As can be seen from FIG. 1 below, the deposition rate of each of the dielectric films was 1.41 Å / cycle.

[0234]

[0235] In addition, the density of the dielectric film was measured using an X-ray reflectometry (XRR) device, and the measured density was 9.83 g / cm 3 It was.

[0236]

[0237] Furthermore, the content of impurities in the dielectric film was measured.

[0238] Here, the impurities are H-, C-, NH-, 18 O-, 30 Measurements were carried out using secondary ion mass spectrometry (SIMS) equipment for Si- and other elements.

[0239] Specifically, when the ion sputtering penetrated the dielectric film in the axial direction and the sputtering time was 50 seconds, which was when there was little contamination in the surface layer of the substrate, the impurity counts were taken into account and the value of the impurity was confirmed from the SIMS graph.

[0240] Among the confirmed SIMS results, the average carbon (C) impurity content in the dielectric film was calculated to be 694 counts / s. In addition, it was confirmed that the content of impurities remaining as process by-products, in addition to carbon, was reduced from 3340 counts / s to 2600 counts / s.

[0241]

[0242] Example 2

[0243] The precursor compound having the structure represented by Formula 4 was placed in a canister maintained at 25°C and supplied to a separate evaporator heated to 150°C at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. The precursor compound vaporized in the evaporator was introduced into a deposition chamber using a vapor flow controller (VFC) for 1 second, and then argon gas was supplied at 3000 sccm for 5 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0244] Next, 5N HI was placed in a canister as a dielectric film activator and supplied to the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature. After the dielectric film activator was introduced into the deposition chamber containing the substrate for 2 seconds, argon gas was supplied at 3000 sccm for 8 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0245] Next, 1000 sccm of ozone was introduced into the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 9 seconds. At this time, the substrate on which the dielectric film was to be formed was heated to 300°C, and the substrate was a Si substrate with SiO2 formed on top.

[0246]

[0247] This process was repeated 200 to 400 times to fabricate a dielectric film at a deposition rate of 1.46 Å / cycle at different deposition temperatures.

[0248] The density of the dielectric film was measured using an X-ray reflectometer (XRR). The measured density was 10.08 g / cm. 3 It was.

[0249]

[0250] Furthermore, the average carbon (C) impurity content in the dielectric film measured using SIMS (Secondary-ion Mass Spectrometry) equipment was calculated to be 243 counts / s. It was also confirmed that the content of not only carbon but also H impurities remaining as a process by-product was reduced.

[0251]

[0252] Comparative Example 1

[0253] The same process as in Example 1 was repeated, except that the dielectric film was manufactured without using 5N HI, which was used as a dielectric film activator in Example 1. The measurement results are shown in Figure 1 below.

[0254] As is clear from FIG. 1 below, the rate of increase in the deposition rate of the dielectric film (rate of increase in D / R (dep. rate)) was 0.84 Å / cycle.

[0255] As a result, it is found that the result is about 33% worse than that of Example 1.

[0256] The density of the dielectric film was measured using an X-ray reflectometry (XRR) device. The average density was 9.71 g / cm. 3 It is found to be inferior to Example 1.

[0257] Furthermore, the impurity content of the dielectric film was measured and confirmed using SIMS. The carbon (C) impurity content in the dielectric film was calculated to be 927 counts / s, which is about 33% lower than that of Example 1.

[0258]

[0259] Comparative Example 2

[0260] The same process as in Example 2 was repeated, except that the dielectric film was manufactured without using 5N HI, which was used as a dielectric film activator in Example 2. The measurement results are shown in Figure 1 below.

[0261] The deposition rate increase rate (D / R (dep. rate) increase rate) of the dielectric film was 0.91 Å / cycle, which was about 60% worse than Example 1.

[0262] The density of the dielectric film was measured using an X-ray reflectometer (XRR). The average density was 10.08 g / cm. 3 It is found to be inferior to Example 1.

[0263] Furthermore, the impurity content of the dielectric film was measured, and the carbon (C) impurity content in the dielectric film confirmed using SIMS was calculated to be 243 counts / s, which is about 42% lower than in Example 1.

[0264]

[0265] From the above results, it was confirmed that the present invention, which uses a dielectric film activator having a predetermined structure, not only significantly improves the deposition thickness, deposition rate, and thin film density compared to the comparative example, which does not use any dielectric film activator, but also improves the dielectric properties due to its excellent impurity reduction properties.

[0266] In particular, Example 1, which used the dielectric film activator according to the present invention, showed excellent results, including an increase in the deposition rate of the dielectric film per cycle of 10% or more, a density of the dielectric film of 10% or more, and a reduction in impurities of 60% or more, even though the dielectric film was prepared under a low-temperature condition of 300°C, compared to Comparative Example 1, which did not use the activator.

[0267]

[0268] Additional Example 1

[0269] A thin film of approximately 13 nm was obtained by repeatedly injecting a precursor (CpHf) into a Si substrate at 300°C, injecting an activator (HI), and reacting with a reactant (O3). Using SIMS (Secondary-ion Mass Spectrometry) analysis, the C impurity value was confirmed by taking into account the C impurity content (counts) in the surface layer of the substrate when the sputtering time was 50 seconds, which is low in contamination, while ion sputtering penetrated the thin film in the axial direction. As can be seen from the graph in Figure 2, the C impurity value was confirmed to be approximately 700 counts / s.

[0270]

[0271] Additional Comparative Example 1

[0272] The precursor (CpHf) was injected into a Si substrate at 300°C, and the process of reacting with a reactant (O3) was repeated to obtain a thin film of approximately 13 nm.

[0273] Using SIMS (Secondary-ion mass spectrometry) analysis, the value of C impurity was confirmed by ion sputtering into the thin film in the axial direction, taking into account the content (counts) of C impurity in the surface layer of the substrate when the sputtering time was 50 seconds, which is low in contamination.As can be seen from the graph in Figure 3, the value was confirmed to be approximately 1100 counts / s.

[0274]

[0275] Therefore, when a specific compound is used as the dielectric film activator of the present invention, the film thickness and deposition rate increase rate, density, and dielectric properties of the dielectric film are all improved, and the impurity reduction properties are also excellent, so it has been confirmed that a dielectric film can be effectively formed even on substrates with complex patterns.

Claims

1. A dielectric film activator characterized by exchanging a first ligand directly bonded to the central metal of a precursor adsorbed on a substrate with a second ligand contained in the dielectric film activator to provide an activated substrate-adsorbed precursor.

2. 2. The dielectric film activator according to claim 1, wherein the central metal of the precursor adsorbed on the substrate is a Group 4 element.

3. 2. The dielectric film activator according to claim 1, wherein the precursor molecule adsorbed on the substrate is selected from the group consisting of a structure represented by the following Chemical Formula 1 and a structure represented by the following Chemical Formula 2: [Chemical formula 1] 【Chemistry 1】 (In the above formula 1, M is Zr or Hf, and R １ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, and X' １ , X' ２ and X' ３ are independently —NR′ １ R' ２ or -OR' ３ , Cl, or F, and said R' １ ~R' ３ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms. [Chemical formula 2] 【Chemistry 2】 (In the above chemical formula 2, the M is Zr or Hf, and the X １ , X ２ are independently -NR １ R ２ or -OR ３ , Cl, or F, and said R １ ~R ３ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, Y is an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.

4. The dielectric film activator according to claim 1 , wherein the first ligand and the second ligand each independently contain a halogen, a halogen and oxygen, a carbon and hydrogen, or a nitrogen and carbon simultaneously.

5. 2. The dielectric film activator of claim 1, wherein the first ligand is the ligand of Formula 1 or Formula 2, and the ligand of the precursor adsorbed on the substrate additionally includes at least one selected from the group consisting of chlorine, fluorine, and bromine, and the dielectric film activator includes at least one halogen selected from the group consisting of iodine and bromine.

6. 2. The dielectric film activator according to claim 1, wherein the dielectric film activator is a mixed gas of hydrogen iodide (HI), hydrogen bromide (HBr), or an inert gas in a molar ratio of 1 to 99.

7. The dielectric film activator according to claim 1, characterized in that the activated substrate-adsorbed precursor promotes reaction with a pre-injected or post-injected reactant gas injected before the precursor, and reduces the content of residual carbon compound impurities.

8. 8. The dielectric film activator according to claim 7, wherein the reduction in the content of residual carbon compound impurities includes a reduction in the content of by-product carbon-oxygen impurities generated by binding of precursor desorbed ligands with reactants, and a reduction in the content of carbon compound impurities that are not desorbed from the precursor.

9. 9. The dielectric film activator according to claim 8, wherein the reduction in the content of the undesorbed carbon compound impurities is due to the replacement of the ligand of the precursor adsorbed on the substrate with the dielectric film activator contained in the dielectric film activator.

10. 2. The dielectric film activator of claim 1, wherein the adsorption state of the precursor before the ligand exchange is represented by the following Chemical Formula 3-1, and the adsorption state of the precursor after the ligand exchange is represented by the following Chemical Formula 3-2. [Chemical formula 3-1] 【Transformation 3】 (In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, and X is a ligand species of Chemical Formula 1, Chemical Formula 2, F, or Cl, and may be different from each other.) [Chemical formula 3-2] 【Chemistry 4】 (In the above chemical formula 3-2, M is Hf or Zr, M is an integer of 1 to 4, and Y is Br or I.)

11. 2. The dielectric film activator of claim 1, wherein the substrate is a silicon wafer, an insulating film, or a dielectric film having a —H or —OH terminal group.

12. 10. The dielectric film activator of claim 1, wherein the dielectric film is a deposited film, and the deposition includes atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), metal-organic chemical vapor deposition (MOCVD), or low-pressure chemical vapor deposition (LPCVD).

13. a substrate and a dielectric film; A semiconductor substrate, wherein the dielectric film is a film deposited using the dielectric film activator according to any one of claims 1 to 7 and claims 10 to 11.

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

15. The dielectric film has a thin film density of 9.5 g / cm ３ 14. The semiconductor substrate according to claim 13, wherein the concentration of carbon impurities measured by secondary ion mass spectrometry (SIMS) is 1000 counts / s or less, and the concentration of iodine atoms measured by secondary ion mass spectrometry (SIMS) is 50 counts / s or more.

16. A semiconductor device comprising the semiconductor substrate of claim 13.

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