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

Abstract

The invention relates to a dielectric film activator, a semiconductor substrate manufactured using the same, and a semiconductor device. According to the present invention, by using a dielectric film activator capable of reducing the content of a by-product carbon compound between a precursor mixed in a dielectric film and a reaction gas and providing a thin film density increasing effect, the capacitance of the dielectric film is improved, and the thin film density increasing effect is provided through a simple process.

Description

Technical Field

[0001] The present invention relates to a dielectric film activator, a semiconductor substrate and a semiconductor device manufactured using the same, and in particular to a dielectric film activator, a semiconductor substrate and a semiconductor device manufactured using the same, which can reduce residual carbon compound impurities between precursors and reaction gases mixed in a dielectric film to improve capacitance and provide a film density increase effect. Background Art

[0002] Dielectrics are insulators that do not conduct electricity like insulators, but exhibit polarity in an electric field. Dielectrics play a very important role in semiconductor devices.

[0003] As an example, the substance that actually stores electricity in a capacitor is a dielectric.

[0004] On the other hand, when a high-k dielectric having a high dielectric constant is mixed with by-produced carbon compounds between the precursor and the reaction gas, a very large capacitance difference may result.

[0005] The residual carbon compound impurity content mixed into the above-mentioned dielectric film, including impurities between the precursor and the reaction gas, is a factor affecting the dielectric properties and chemical properties, which will reduce the dielectric constant. Or when the dielectric film absorbs by-products (HCl, hydrocarbons) from the leaving group of the halogen ligand and is contaminated or the crystal arrangement of the dielectric film is disturbed, the film density will be reduced and the dielectric constant will be reduced.

[0006] Therefore, it is necessary to develop a dielectric film activator that can reduce the content of residual carbon compound impurities mixed into the dielectric, including impurities between the precursor and the reaction gas, and increase the film density to provide an effect of improving the dielectric constant, as well as a dielectric film manufacturing method using the same, a semiconductor substrate and a semiconductor device manufactured thereby, etc.

[0007] Prior art literature

[0008] Patent Literature

[0009] U.S. Patent Publication No. 2020 / 0316645 (Publication Date: 2020.10.08.) Summary of the invention

[0010] Problem that the invention aims to solve

[0011] In order to solve the technical problems in the prior art as described above, the purpose of the present invention is to activate the precursor adsorbed on the substrate using a dielectric film activator of a predetermined structure to prevent by-product carbon compounds between the precursor and the reaction gas from mixing into the dielectric film, thereby providing a high-quality dielectric film with increased capacitance and increased film density, and further providing a semiconductor substrate and a semiconductor device including the dielectric film.

[0012] The above-mentioned object and other multiple objects of the present invention can be fully achieved by the present invention described below.

[0013] Means used to solve problems

[0014] To achieve the above object, the present invention provides a dielectric film activator, which uses a second ligand contained in the dielectric film activator to replace a first ligand directly connected to a central metal of a substrate adsorption precursor to provide an activated substrate adsorption precursor.

[0015] As an example, the central metal of the above-mentioned precursor may be a Group IV element.

[0016] As a specific example, the central metal of the above-mentioned precursor may be Hf or Zr.

[0017] The precursor molecule adsorbed on the substrate may be one or more 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.

[0018] [Chemical formula 1]

[0019]

[0020] (In the above chemical formula 1, the above M is Zr or Hf, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, the above 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 the above R'1 to R'3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms.)

[0021] [Chemical formula 2]

[0022]

[0023] (In the above chemical formula 2, the above M is Zr or Hf, the above X1 and X2 are independently -NR1R2 or -OR3, Cl or F, the above R1 to R3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, the above Y is an alkyl group having 1 to 6 carbon atoms, and the above n is 1 or 2.)

[0024] The precursor molecule adsorbed on the substrate may have a structure in which a central metal is bound to four ligands independently selected from -NR'1R'2 or -OR'3, Cl or F. 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.

[0025] The first ligand and the second ligand may each independently contain a halogen, or contain a halogen and oxygen, or carbon and hydrogen, or contain nitrogen and carbon.

[0026] The first ligand may be a ligand of the chemical formula 1 or 2, the ligand of the precursor adsorbed on the substrate may further include one or more selected from chlorine, fluorine, and bromine, and the dielectric film activator may contain one or more halogens selected from iodine and bromine.

[0027] The dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas of hydrogen iodide (HI) or hydrogen bromide (HBr) mixed with an inert gas at a molar fraction of 1 to 99.

[0028] The activated precursor adsorbed on the substrate promotes the reaction with the reaction gas injected before or after the precursor and reduces the content of residual carbon compound impurities.

[0029] The reduction in the residual carbon compound impurity content may include: a reduction in the by-product carbon-oxygen compound impurity content generated by the combination of the precursor desorption ligand and the reaction gas and a reduction in the carbon compound impurity content that is not desorbed from the precursor.

[0030] The reduction in the content of the non-desorbed 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.

[0031] The reaction gas may be one or more selected from H2O, H2O2, N2O, NO2, O2, O3 and O radicals.

[0032] The adsorption state of the precursor before the ligand is replaced can be represented by Chemical Formula 3-1, and the adsorption state of the precursor after the ligand is replaced can be represented by Chemical Formula 3-2.

[0033] [Chemical formula 3-1]

[0034] Substrate-MX n

[0035] (In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, and X is the type of ligand in Chemical Formula 1, the type of ligand in Chemical Formula 2, F or Cl, and they are different from each other.)

[0036] [Chemical formula 3-2]

[0037] Substrate-MY m

[0038] (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.)

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

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

[0041] Among them, deposition may include 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).

[0042] In addition, the present invention provides a semiconductor substrate including a substrate and a dielectric film, wherein the dielectric film is a film deposited using the dielectric film activator.

[0043] The dielectric film may have a multi-layer structure of two or more layers.

[0044] The deposition rate of the above dielectric film measured on SiO2 or Si (based on the film deposited at 300°C) can be / cycle or above.

[0045] The film density of the above dielectric film measured on SiO2 or Si can be 9.8 g / cm 3 above.

[0046] The C impurity content of the above dielectric film measured on SiO2 or Si using SIMS (based on a film deposited at 300°C) may be 1000 counts / s.

[0047] In addition, the present invention provides a semiconductor device, which includes the semiconductor substrate mentioned above.

[0048] Effects of the Invention

[0049] According to the present invention, a dielectric film activator is provided, which can promote the reaction with a post-injected reaction gas through an activated precursor adsorbed on a substrate and reduce the residual carbon compound impurity content.

[0050] Specifically, when forming a dielectric film, the density is improved and process byproducts are more effectively reduced, thereby preventing corrosion and degradation, and having the effect of improving the dielectric characteristics of the dielectric film.

[0051] In addition, the thickness uniformity of the dielectric film can be improved, thereby having the effect of providing a dielectric film manufacturing method using the dielectric film activator, and a semiconductor substrate and a semiconductor device manufactured thereby. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1This is a graph comparing the growth rates of the dielectric film of Example 1 using a dielectric film activator according to the present invention at different deposition temperatures and the growth rates of the dielectric film of Comparative Example 1 not using a dielectric film activator at different deposition temperatures.

[0053] Figure 2 FIG. 1 is a graph showing the C impurity content of the dielectric film of Additional Example 1 using a dielectric film activator according to the present invention, obtained by SIMS analysis.

[0054] Figure 3 : is a graph showing the C impurity content of the dielectric film of Comparative Example 1 added without using a dielectric film activator, obtained by SIMS analysis. DETAILED DESCRIPTION

[0055] Hereinafter, the dielectric film activator of the present invention, and the semiconductor substrate and semiconductor device produced using the same will be described in detail.

[0056] The inventors of the present invention have confirmed that the use of a dielectric film activator that can reduce the content of by-product carbon-oxygen compound impurities generated by the combination between the precursor desorption ligand and the reactant mixed in the dielectric film and the content of carbon compound impurities not desorbed from the above precursor and provide a film density increase effect can improve the density and prevent corrosion and degradation when forming a dielectric film, improve the dielectric properties of the dielectric film, and improve the thickness uniformity of the dielectric film, thereby providing a high-quality dielectric film. Based on this, the inventors have studied dielectric films and completed the present invention.

[0057] Hereinafter, a dielectric film activator, a semiconductor substrate including a dielectric film manufactured using the same, and a semiconductor device will be described in detail.

[0058] In the present invention, the dielectric film activator may be a substrate-adsorbed precursor activated by activating the precursor adsorbed on the substrate in the present invention, thereby promoting the reaction with the post-injected reaction gas and reducing the residual carbon compound impurities mixed into the dielectric film.

[0059] The central metal of the precursor adsorbed on the substrate is a Group IV element, and the ligand may contain two or more halogens that are the same or different from each other and adsorbed on the substrate.

[0060] Preferably, the central metal may be Hf or Zr.

[0061] In the present invention, the precursor compound used to form the dielectric film can be Hf(NMe2)4, Zr(NMe2)4, CpZr(CpZr(NMe2)3), CpHf(CpHf(NMe2)3) formed by Hf and Zr as Group IV metals, and their derivatives with Hf and Zr as central metals, and can be linear or cyclic precursor molecules formed by connecting multiple ligands bound to the central metal.

[0062] As an example, the precursor molecules adsorbed on the substrate may be represented by the following Chemical Formula 1 and the following Chemical Formula 2.

[0063] [Chemical formula 1]

[0064]

[0065] (In the above chemical formula 1, the above M is Zr or Hf, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, the above 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 the above R'1 to R'3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms.)

[0066] [Chemical formula 2]

[0067]

[0068] (In the above chemical formula 2, the above M is Zr or Hf, the above X1 and X2 are independently -NR1R2 or -OR3, Cl or F, the above R1 to R3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, the above Y is an alkyl group having 1 to 6 carbon atoms, and the above n is 1 or 2.)

[0069] As a molecule having a transition metal as the central metal atom (M) and having one or more ligands composed of C, N, O, H, X (halogen), a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25°C can maximize the effect of replacing the ligand with a dielectric film activator described later.

[0070] In addition, zirconium precursor compounds such as tris(dimethylamido)cyclopentadienyl zirconium (CpZr(NMe2)3), (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)zirconium (Cp(CH2)3NM3Zr(NMe2)2), tetrakis(ethylmethylamido)zirconium ([(Me)(Et)N]4Zr), etc. can be used. In this case, the dielectric film activator described later can be appropriately filled.

[0071] Hafnium precursor compounds, for example, tris(dimethylamido)cyclopentadienyl hafnium (CpHf(NMe2)3), (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium (Cp(CH2)3NM3Hf(NMe2)2), tetrakis(ethylmethylamido)hafnium ([(Me)(Et)N]4Hf), etc., can be used. At this time, they can be appropriately filled with the above-mentioned dielectric film activators.

[0072] In the present invention, as an example, the precursor compound may be introduced into the chamber in a mixed state with a non-polar solvent. In this case, there is an advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0073] Preferably, the non-polar solvent may be one or more selected from alkanes and cycloalkanes. In this case, the non-polar solvent may include an organic solvent having low reactivity and solubility and easy moisture management, and has the advantage of being able to increase the film density even when the deposition temperature is increased when forming a dielectric film.

[0074] As a more preferred example, the non-polar solvent may include C1 to C 10 Alkanes or C3~C 10 Cycloalkane, preferably C3~C 10 Cycloalkane has the advantages of low reactivity and solubility and easy water management.

[0075] In the present invention, C1, C3, etc. represent the number of carbon atoms.

[0076] Preferably, the cycloalkane may be C3 to C 10 Among the above monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure. Therefore, it is preferred in the vapor deposition process, but is not limited to this.

[0077] As an example, the solubility of the non-polar solvent in water (25° C.) is less than 200 mg / L, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantages of low reactivity to precursor compounds and easy water management.

[0078] In the present invention, the solubility is not particularly limited as long as it is based on the measurement method and standard conventionally used in the art. As an example, a saturated solution can be measured by HPLC.

[0079] Based on the total weight of the precursor compound and the non-polar solvent, the content of the non-polar solvent may preferably be 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.

[0080] If the content of the above-mentioned non-polar solvent is greater than the above-mentioned upper limit, impurities will be induced, thereby causing an increase in the impurity values ​​in the resistor and dielectric film. When the content of the above-mentioned organic solvent is less than the above-mentioned lower limit, there are disadvantages that the effect of increasing the film density by adding the solvent and the effect of reducing impurities such as chloride (Cl) ions are not obvious.

[0081] The first ligand and the second ligand may each independently contain a halogen, or contain a halogen and oxygen, or carbon and hydrogen, or contain nitrogen and carbon.

[0082] The first ligand may be a ligand of the chemical formula 1 or 2, the ligand of the precursor adsorbed on the substrate may further include one or more selected from chlorine, fluorine, and bromine, and the dielectric film activator may contain one or more halogens selected from iodine and bromine.

[0083] The dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas of hydrogen iodide (HI) or hydrogen bromide (HBr) mixed with an inert gas at a molar fraction of 1 to 99.

[0084] A substance having a structure in which these central metals and the above-mentioned ligands are bonded can be used as a precursor adsorbed on a substrate, and activated by the above-mentioned dielectric film activator to obtain an activated precursor adsorbed on a substrate.

[0085] The activated substrate adsorbed precursor can promote the reaction with the post-injected reaction gas and reduce the residual carbon compound impurity content.

[0086] The reduction of the residual carbon compound impurity content may include: the reduction of the by-product carbon-oxygen compound impurity content generated by the combination of the precursor desorption ligand and the reactant and the reduction of the carbon compound impurity content not desorbed from the precursor.

[0087] Specifically, the reduction in the content of the non-desorbed carbon compound impurities is caused by replacing the ligand of the precursor adsorbed on the substrate with the dielectric film activator contained in the dielectric film activator.

[0088] The adsorption state of the precursor before the ligand is replaced can be represented by the following chemical formula 3-1, and the adsorption state of the precursor after the ligand is replaced can be represented by the following chemical formula 3-2.

[0089] [Chemical formula 3-1]

[0090] Substrate-MX n

[0091] (In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, and X is the type of ligand in Chemical Formula 1, the type of ligand in Chemical Formula 2, F or Cl, and they are different from each other.)

[0092] [Chemical formula 3-2]

[0093] Substrate-MY m

[0094] (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.)

[0095] As an example, when the precursor adsorbed on the substrate is CpHf(NMe2)3, the structure of the precursor adsorbed on the substrate activated by the dielectric film activator is: n ), M is Hf, and X, which may be different from each other, is one Cp ligand and two NMe2 ligands.

[0096] The substrate may be a silicon wafer, an insulating film or a dielectric film containing -H or -OH terminal groups.

[0097] As an example, the ligand of the precursor adsorbed on the substrate may be a ligand species having a structure represented by the above Chemical Formula 1 or Chemical Formula 2, or may be F or C.

[0098] As another example, the ligand of the precursor adsorbed on the substrate may be independently selected from -NR'1R'2 or -OR'3, Cl or F, wherein R'1 to R'3 may be independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0099] When the precursor adsorbed on the substrate contains one or more halogens selected from chlorine, fluorine, nitrides and carbon compounds, the dielectric film activator is preferably a nitride and a carbon compound reacting with an iodine activator and a bromine activator compared to chlorine and fluorine.

[0100] As a specific example, the dielectric film activator may be hydrogen iodide (HI), hydrogen bromide (HBr), or a mixed gas obtained by mixing hydrogen iodide (HI) or hydrogen bromide (HBr) in an inert gas at a molar fraction of 1 to 99.

[0101] 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 smoothly replacing the ligand.

[0102] At this time, side reactions can be suppressed to reduce process byproducts in the dielectric film, thereby reducing corrosion and degradation, and controlling the film growth rate to achieve a stoichiometric oxidation state when forming a metal oxide film, and having the effect of greatly improving the thickness uniformity of the dielectric film.

[0103] As a specific example, the above-mentioned dielectric film activator is pure 3N~15N hydrogen iodide, or a gas mixture of 1~99 weight % of 3N~15N hydrogen iodide and an inert gas with the remainder making the total amount reach 100 weight %, or an aqueous solution mixture of 0.5~70 weight % of 3N~15N hydrogen iodide and water with the remainder making the total amount reach 100 weight %, among which, when the inert gas is nitrogen, helium or argon with a purity of 4N~9N, the effect of reducing process by-products is significant, and the effect of improving film density is excellent, and the film density improvement effect and the electrical properties of the film are more outstanding.

[0104] Preferably, the dielectric film activator may be pure 5N-6N hydrogen iodide, or a gas mixture of 1-99 wt% 5N-6N hydrogen iodide and an inert gas with the remainder making the total amount reach 100 wt% or an aqueous solution mixture of 0.5-70 wt% 5N-6N hydrogen iodide and water with the remainder making the total amount reach 100 wt%. The inert gas may be nitrogen, helium or argon with a purity of 4N-9N. In this case, side reactions can be suppressed and the film growth rate can be adjusted to reduce process byproducts in the film, thereby reducing corrosion and degradation, and improving the crystallinity of the film. Even if a film is formed on a substrate with a complex structure, the film density and the thickness uniformity of the film can be greatly improved.

[0105] Preferably, the above-mentioned dielectric film activator can be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, when a compound with a purity of less than 99% is used, impurities may remain in the dielectric film or cause side reactions with precursors or reactants. Therefore, substances with a purity of 99% or more should be used as much as possible.

[0106] The vapor pressure under the condition of 180-240K can be one atmosphere. Within this range, the material can be smoothly transported into the chamber, so the thickness uniformity, dielectric properties and film quality of the dielectric film are improved.

[0107] The present invention may include the following steps: after injecting the dielectric film activator in a gaseous state and gasifying and injecting the above-mentioned precursor compound, plasma post-treatment is performed. In this case, the growth rate of the dielectric film can be improved and process byproducts can be reduced.

[0108] The above-mentioned thin films (including dielectric films) may be deposited films.

[0109] The above deposition can be 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).

[0110] The reaction gas may be one or more selected from H2O, H2O2, N2O, NO2, O2, O3 and O radicals.

[0111] The above-mentioned dielectric film can be produced by various methods, and as an example, can be produced by the following method.

[0112] As a first step, a precursor compound having a ligand on the transition metal that is an alkyl, alkylamine or halogen, or a combination of halogen and oxygen, or carbon and hydrogen, or a combination of nitrogen and carbon may be injected onto the substrate loaded into the chamber.

[0113] The ligand may be one or more selected from the group consisting of an alkyl group, an alkylamine, chlorine, and fluorine, and is preferably an alkylamine having excellent reactivity.

[0114] The structure containing both carbon and hydrogen may be, for example, a cyclopentadienyl group (Cp).

[0115] In the present invention, as an example, the method of delivering precursor compounds to the deposition chamber can adopt a flow control method (Mass Flow Controller; MFC) including a method of delivering volatile gas (Vapor Flow Control; VFC) using a vapor phase flow control method (Mass Flow Controller; MFC), a liquid phase flow control method (Liquid Mass Flow Controller; LMFC), and a liquid delivery method (Liquid Delivery System; LDS).

[0116] At this time, as a carrier gas or dilution gas for transporting the precursor compound to the substrate, one or a mixed gas of two or more selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited thereto.

[0117] In the present invention, as an example, an inert gas may be used as the purge gas, and preferably, the above-mentioned carrier gas or diluent gas may be used.

[0118] The above-mentioned chamber can be an atomic layer deposition (ALD) chamber, a plasma assisted atomic layer deposition (PEALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced chemical vapor deposition (PECVD) chamber, an organic metal chemical vapor deposition (MOCVD) chamber or a low pressure chemical vapor deposition (LPCVD) chamber.

[0119] The substrate loaded in the chamber may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0120] The substrate may further have a conductive layer or an insulating layer formed on an upper portion thereof.

[0121] The substrate may be maintained at 50 to 500°C or 80 to 500°C.

[0122] As an example, the substrate may be heated to 50-500°C, and as a specific example, may be heated to 80-500°C, 100-800°C, or 200-500°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, it is possible to heat the substrate during the deposition process after injecting the dielectric film in an unheated state. As an example, the dielectric film activator or precursor compound may be injected onto the substrate at 50-500°C for 1-20 seconds.

[0123] As an example, the ratio of the amount (mg / cycle) of the dielectric film activator used in the second step described later to the amount of the above-mentioned precursor compound added into the chamber is 1:1 to 1:100, preferably 1:1 to 1:50, and more preferably 1:1 to 1:25. Within this range, the effect of improving the film density and reducing the process by-products is significant.

[0124] The first step may include one or more steps of purging with an inert gas. The inert gas may be the carrier gas or the diluent gas.

[0125] In the step of purging the unadsorbed precursor compound, the amount of the 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 can 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 the film quality from being deteriorated. The amounts of the purge gas and the precursor compound introduced are based on one cycle, respectively, and the volume of the precursor compound represents the volume of the vaporized precursor compound vapor.

[0126] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or a manner close thereto, which is advantageous in terms of film quality.

[0127] As a second step, a dielectric film activator is injected into the substrate to replace the leaving group of the precursor adsorbed on the substrate with the halogen of the activator. At this time, the leaving group of the precursor adsorbed on the substrate is effectively changed to the halogen of the activator to form a film without lattice gaps, thereby improving the film density, and thus having the effect of greatly improving the dielectric properties and the thickness uniformity of the film.

[0128] As an example, the halogen may be one or more selected from iodine and bromine, and iodine is preferably used.

[0129] The feeding time (Feeding Time, sec) of the dielectric film activator to the surface of the above-mentioned substrate in each cycle is preferably 0.01 to 10 seconds, more preferably 0.02 to 3 seconds, more preferably 0.04 to 2 seconds, and further preferably 0.05 to 1 second. Within this range, it has the advantages of low film growth rate, improved film density and excellent economy.

[0130] In the present invention, the supply amount of the dielectric film activator is based on a flow rate of 1 to 300 sccm / cycle at a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 10 to 100 sccm / cycle at a chamber volume of 18 L.

[0131] In the present invention, as an example, the method of delivering the dielectric film activator to the deposition chamber may be a method of delivering gas using a Mass Flow Controller (MFC) method.

[0132] The second step may include one or more steps of purging with an inert gas. In the present invention, as an example, the purge gas may be the carrier gas or the diluent gas.

[0133] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or a manner close thereto, which is advantageous in terms of film quality.

[0134] In the step of purging the non-absorbed dielectric film activator, the amount of the purge gas introduced into the chamber is not particularly limited as long as it is sufficient to remove the non-absorbed dielectric film activator. For example, it can be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the non-absorbed dielectric film activator can be sufficiently removed to form a uniform thin film and prevent the film quality from being deteriorated. The amounts of the purge gas and the dielectric film activator introduced are based on one cycle, respectively, and the volume of the dielectric film activator represents the volume of the vaporized dielectric film activator vapor.

[0135] As a specific example, when the above-mentioned dielectric film activator is injected at a flow rate of 100 sccm and an injection time of 0.5 sec (per cycle), and in the step of purging the unadsorbed dielectric film activator, the purge gas is injected at a flow rate of 3000 sccm and an injection time of 5 sec (per cycle), the injection amount of the purge gas is 300 times the injection amount of the dielectric film activator.

[0136] Next, as a third step, a reaction gas may be injected into the substrate to form a thin film composed of transition metals and heteroatoms.

[0137] The reaction gas may be, for example, one or more selected from H2O, H2O2, N2O, NO2, O2, O3 and O radicals.

[0138] The above-mentioned thin film may include a structure in which the Group IV metal and the halogen are directly bonded.

[0139] As an example, the above-mentioned dielectric film forming method can be implemented at a deposition temperature in the range of 50°C to 800°C, preferably, in the range of 100°C to 700°C, more preferably, in the range of 200°C to 650°C, and even more preferably, in the range of 220°C to 500°C. Within this range, it has the effect of realizing process characteristics and growing a thin film with excellent film quality.

[0140] As an example, the above-mentioned dielectric film forming method can be implemented 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, the effect of obtaining a thin film with uniform thickness can be achieved.

[0141] In the present invention, the deposition temperature and the deposition pressure may be measured by the temperature and pressure formed in the deposition chamber or by the temperature and pressure applied to the substrate in the deposition chamber.

[0142] Preferably, the second step may further include the following steps: before adding the dielectric film activator into the chamber, raising the temperature in the chamber to the deposition temperature; and / or before adding the dielectric film activator into the chamber, injecting an inactive gas into the chamber for purging.

[0143] The third step may include a step of purging with an inert gas.

[0144] In the purge step performed immediately after the reaction gas supply step, as an example, the amount of the purge gas introduced into the chamber 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 reaction gas introduced into the chamber. Within this range, the desired effect can be fully obtained. The amounts of the purge gas and the reaction gas introduced are based on one cycle, respectively.

[0145] In the present invention, the purge is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or a manner close thereto, which is advantageous in terms of film quality.

[0146] As an example, in the above-mentioned dielectric film forming method, the number of repetitions of the unit cycle can be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, as needed. Within this range, the desired film thickness can be obtained, the content of by-product carbon compounds can be reduced, and the film density can be improved.

[0147] As a specific example of the dielectric film manufacturing method, the dielectric film activator and the precursor compound or a mixture thereof with a non-polar solvent are prepared separately to deposit the dielectric film on the substrate placed in the chamber.

[0148] Thereafter, after the prepared precursor compound or a mixture thereof with a non-polar solvent is injected into the vaporizer, it is changed into a vapor phase so as to be transported to the deposition chamber and adsorbed on the substrate, the ligand of the above-mentioned precursor compound is replaced by a dielectric film activator, and the non-adsorbed precursor compound is purged.

[0149] Next, after the prepared dielectric film activator is injected into the vaporizer, it is changed into a vapor phase to be transported to the deposition chamber and adsorbed on the substrate, and then purging is performed to remove the non-adsorbed dielectric film activator.

[0150] In the present invention, as an example, the method of delivering the dielectric film activator and the precursor compound to the deposition chamber may be a method of delivering gas using a Mass Flow Controller (MFC) method (Vapor Flow Control; VFC).

[0151] At this time, as a carrier gas or dilution gas for transporting dielectric film activators and precursor compounds to the substrate, one or a mixed gas selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited to this.

[0152] In the present invention, as an example, an inert gas may be used as the purge gas, and preferably, the above-mentioned carrier gas or diluent gas may be used.

[0153] Next, a heteroatom-containing gas is supplied. The heteroatom-containing gas is not particularly limited as long as it is a conventional reaction gas in the art, and preferably, it may contain an oxidant. The oxidant reacts with the precursor compound adsorbed on the substrate to form an oxide film.

[0154] Preferably, the oxidant may be oxygen (O2), ozone (O3) or a mixture of nitrogen and oxygen.

[0155] Next, the unreacted residual reaction gas is purged with an inert gas, thereby removing not only the excess reaction gas but also the generated by-products.

[0156] As described above, as an example, the above-mentioned dielectric film forming method can take the following steps as a unit cycle and repeat the above-mentioned unit cycle to form a dielectric film of a desired thickness: a step of adsorbing a precursor compound on a substrate; a step of purging the unadsorbed precursor compound; a step of supplying a dielectric film activator to the substrate; a step of purging the unadsorbed dielectric film activator; a step of supplying a reaction gas; and a step of purging the residual reaction gas.

[0157] As an example, the number of repetitions of the unit period may be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired dielectric film properties can be well expressed.

[0158] When the injection time and the purge time of the precursor compound in the first step are set to a and b respectively, and the injection time and the purge time of the alkyl free halide in the second step are set to c and d respectively, and the injection time and the purge time of the heteroatom-containing gas in the third step are set to e and f respectively, 0.1≤a≤10, 2a≤b≤4a, 0.1 <c≤10、2c≤d≤8c、2<e≤10、2e≤b≤8e。

[0159] When the injection and purge of the above-mentioned precursor compound and dielectric film activator, and the injection and purge of the heteroatom-containing gas are set as one cycle, the following two conditions can be met at the same time: 1) The deposition rate of the above-mentioned dielectric film on SiO2 is / cycle or more, 2) the density of the dielectric film is 9.8g / cm 3 above.

[0160] When the injection and purge of the above-mentioned precursor compound and dielectric film activator, and the injection and purge of the heteroatom-containing gas are set as one cycle, the following two conditions can be satisfied at the same time: 1) the deposition rate of the above-mentioned dielectric film on SiO2 is / cycle, 2) the density of the dielectric film is 9.8~10.5g / cm 3 .

[0161] As an example, the dielectric film manufacturing method can be implemented using a dielectric film manufacturing apparatus, the dielectric film manufacturing apparatus comprising an ALD chamber, a corrosion-resistant MFC including a gold seal capable of quantitatively injecting a dielectric film activator, a first transport unit for transporting the quantitatively injected dielectric film activator into the ALD chamber, a second vaporizer for vaporizing a precursor adsorbed on a substrate, and a second transport unit for transporting the vaporized precursor adsorbed on the substrate into the ALD chamber. The vaporizer and the transport unit are not particularly limited, as long as they are conventionally used in the art.

[0162] Including thin films deposited using the above-mentioned dielectric film activator.

[0163] The above-mentioned thin film may be a dielectric film.

[0164] The above-mentioned film may be a multi-layer structure of two or more layers.

[0165] As an example, the above-mentioned thin film can be obtained by the reaction between the activated substrate adsorption precursor represented by the structure of the above-mentioned chemical formula 1 and the reaction gas. At this time, by using the activated substrate adsorption precursor, the content of by-product carbon compounds can be reduced, thereby manufacturing a high-quality thin film.

[0166] As an example, the reduction of the by-produced carbon compounds between the activated precursor adsorbed on the substrate and the reaction gas is due to the activation energy of the activated precursor adsorbed on the substrate being smaller than the activation energy of the precursor adsorbed on the substrate.

[0167] The deposition rate of the above dielectric film on SiO2 or Si measured by ellipsometer (based on the film deposited at 300°C) can be / cycle or more, or / cycle, within the above range, can improve thin film uniformity and deposition productivity.

[0168] The film density of the above dielectric film measured on SiO2 or Si can be 9.5g / cm 3 Above, 9.8g / cm 3 Above, or 9.8~10.3g / cm 3 , within the above range, the dielectric properties can be improved.

[0169] The carbon impurity content of the above-mentioned dielectric film measured on SiO2 or Si using SIMS (based on the film deposited at 300°C) can be less than 1000 counts / second, less than 715 counts / second or less than 700 counts / second. Within the above range, the leakage of electrons can be significantly reduced, thereby improving the dielectric properties.

[0170] The iodine atom count of the dielectric film measured by SIMS may be 50 counts / second or more or 65 counts / second or more. Within the above range, the film density can be increased, thereby providing an effect of improving the dielectric constant.

[0171] The deposition thickness of the above-mentioned dielectric film measured on SiO2 or Si using SIMS (based on the thin film deposited at 400°C) can be less than 410 counts / second or less than 300 counts / second. Within the above range, the leakage of electrons can be significantly reduced, thereby improving the dielectric properties.

[0172] The dielectric film may include the above-mentioned film components alone or in a selective area, but is not limited thereto and may also include Si, SiH, SiOH, and SiO2.

[0173] The above-mentioned dielectric film can be used not only for a commonly used DRAM but also for a semiconductor device as a dielectric film or an insulating film of a NAND or logic device.

[0174] As an example, the content of the halogen compound in the dielectric film measured using SIMS may be 30,000 counts / second or less.

[0175] The present invention also provides a semiconductor substrate, which is manufactured by the dielectric film forming method of the present invention or includes the above-mentioned dielectric film. At this time, the film density improvement effect and thickness uniformity of the dielectric film are very excellent, and the density and dielectric properties of the dielectric film are excellent.

[0176] Preferably, the deposition rate of the above-mentioned dielectric film on SiO2 is / cycle and above and density 9.8g / cm 3 In the above range, the film has excellent performance as a diffusion prevention film, and has an effect of improving dielectric properties, but is not limited thereto.

[0177] As an example, the impurity halogen remaining in the dielectric film may be Cl2, Cl or Cl - The lower the residual halogen content in the dielectric film, the better the film quality, so it is preferred.

[0178] In addition, the lower the residual carbon content in the dielectric film is, the better the dielectric properties are, which is preferred.

[0179] As an example, the dielectric film may be a multilayer structure of more than two layers, a multilayer structure of more than three layers, or a multilayer structure of two or three layers, as required. As a specific example, the multilayer film of the two-layer structure may be a structure of a lower film-middle film, and as a specific example, the multilayer film of the three-layer structure may be a structure of a lower film-middle film-upper film.

[0180] As an example, the above-mentioned lower layer film may include one or more selected from Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0181] As an example, the intermediate layer film may include Ti x N y , preferably, may contain TN.

[0182] As an example, the upper layer film may include one or more selected from W and Mo.

[0183] According to the present invention, a semiconductor device including the above-mentioned semiconductor substrate can be provided.

[0184] The semiconductor device may be, for example, 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) or a 3D NAND flash memory.

[0185] Below, preferred embodiments and drawings are proposed to help understand the present invention. Those skilled in the art will understand that the following embodiments and drawings are only used to illustrate the present invention, and various changes and modifications can be made within the scope of the scope of the present invention and technical ideas, and these deformations and modifications fall within the scope of the attached claims.

[0186] [Example]

[0187] 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 are prepared as precursor compounds.

[0188] [Chemical Formula 1-1] (Cyclopentadienyl ligand precursor)

[0189]

[0190] [Chemical Formula 4] (Alkylamine ligand precursor)

[0191]

[0192] Prepare 5N HI as a dielectric film activator.

[0193] The ALD deposition process is performed using the above-mentioned precursor compound and dielectric film activator and in accordance with the deposition process sequence of the present invention as one cycle.

[0194] The specific experimental methods of Example 1, Example 2 and Comparative Examples 1 and 2 are as follows.

[0195] Example 1

[0196] The precursor compound having the structure represented by the above chemical formula 1-1 was loaded into a tank maintained at 25° C. and supplied to a separate vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. After the precursor compound vaporized into a vapor phase in the vaporizer was put into the deposition chamber within 1 second using a vapor flow controller (VFC), argon gas was supplied at 3000 sccm for 5 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0197] Next, 5N HI was placed in a tank as a dielectric film activator and supplied to the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature. The dielectric film activator was added to the deposition chamber loaded with the substrate for 2 seconds, and then argon was supplied at 3000 sccm for 8 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0198] Next, ozone was introduced into the reaction chamber as a reactive gas at 1000 sccm for 3 seconds, followed by argon purge for 9 seconds. At this time, the substrate on which the dielectric film was to be formed was heated to 300° C., and SiO2 was formed on the upper part of the Si substrate.

[0199] This process is repeated 200 to 400 times to show Figure 1 The dielectric films were fabricated with different deposition rates at different deposition temperatures.

[0200] like Figure 1 As shown, the deposition rate of the above dielectric film is / cycle.

[0201] In addition, the density of the dielectric film was measured using an X-ray reflectometry (XRR) device. The measured density was 9.83 g / cm 3 .

[0202] Furthermore, the impurity content of the above dielectric film was measured.

[0203] Among them, the secondary ion mass spectrometry (SIMS) equipment was used to measure the H-, C-, NH-, 18 O-, 30 Si- and other impurities.

[0204] Specifically, the impurity content (counts) was considered when the sputtering time was 50 seconds, which was less contamination in the substrate skin layer, by digging into the dielectric film in the axial direction using ion sputtering, and the impurity value was confirmed in the SIMS graph.

[0205] Among the confirmed SIMS results, the average impurity content of carbon (C) in the dielectric film was calculated to be 694 counts / second. In addition to carbon, the impurity content of H remaining as a process byproduct was also confirmed to have decreased from 3340 counts / second to 2600 counts / second.

[0206] Example 2

[0207] The precursor compound having the structure represented by the above chemical formula 4 was loaded into a tank maintained at 25° C. and supplied to a separate vaporizer heated to 150° C. at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. After the precursor compound vaporized into a vapor phase in the vaporizer was put into the deposition chamber within 1 second using a vapor flow controller (VFC), argon gas was supplied at 3000 sccm for 5 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0208] Next, 5N HI was placed in a tank as a dielectric film activator and supplied to the chamber at 100 sccm / cycle using a mass flow controller (MFC) at room temperature. The dielectric film activator was added to the deposition chamber loaded with the substrate for 2 seconds, and then argon was supplied at 3000 sccm for 8 seconds to perform argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0209] Next, ozone was introduced into the reaction chamber as a reactive gas at 1000 sccm for 3 seconds, followed by argon purge for 9 seconds. At this time, the substrate on which the dielectric film was to be formed was heated to 300° C., and SiO2 was formed on the upper part of the Si substrate.

[0210] This process was repeated 200 to 400 times to produce dielectric films at different deposition rates at different deposition temperatures. / cycle.

[0211] In addition, the density of the dielectric film was measured using an X-ray reflectometry (XRR) device. The measured density was 10.08 g / cm 3 .

[0212] Furthermore, the average impurity content of carbon (C) in the dielectric film was measured and calculated using a secondary ion mass spectrometry (SIMS) device to be 243 counts / second. In addition, in addition to carbon, the content of H impurities remaining as a process byproduct was also confirmed to have decreased.

[0213] Comparative Example 1

[0214] The same process as in Example 1 was repeated except that the dielectric film was produced without using 5N HI as a dielectric film activator, and the measurement results are shown together in FIG. Figure 1 middle.

[0215] like Figure 1 As shown, the deposition rate increase rate (D / R (dep.rate) increase rate) of the above dielectric film is / cycle.

[0216] It can be seen that the result is about 33% worse than that of Example 1.

[0217] In addition, 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 can be seen that it is not as good as Example 1.

[0218] Furthermore, the impurity content of the dielectric film was measured, and the carbon (C) impurity content in the dielectric film was confirmed and calculated using SIMS to be 927 counts / second, which was about 33% lower than that of Example 1.

[0219] Comparative Example 2

[0220] The same process as in Example 2 was repeated except that the dielectric film was produced without using 5N HI as a dielectric film activator, and the measurement results are shown together in FIG. Figure 1 middle.

[0221] The deposition rate increase rate (D / R (dep.rate) increase rate) of the above dielectric film is / cycle, it can be seen that the result is about 60% worse than that of Example 1.

[0222] In addition, the density of the dielectric film was measured using an X-ray reflectometry (XRR) device. The average density was 10.08 g / cm 3 , it can be seen that it is not as good as Example 1.

[0223] Furthermore, the impurity content of the dielectric film was measured, and the carbon (C) impurity content in the dielectric film was confirmed and calculated using SIMS to be 243 counts / second, which was approximately 42% lower than that of Example 1.

[0224] Based on the above results, it can be confirmed that according to the present invention using a dielectric film activator having a predetermined structure, the deposition thickness, deposition rate and film density are significantly improved compared to multiple comparative examples that do not use a dielectric film activator at all, and the impurity reduction characteristics are excellent, thereby also improving the dielectric characteristics.

[0225] In particular, it was confirmed that even when the dielectric film was manufactured under low temperature conditions of 300°C, the dielectric film deposition rate increase rate per cycle and the density of the dielectric film were both higher by more than 10%, and the impurity reduction rate was higher by more than 60%, compared with the comparative example 1 which did not use the dielectric film activator of the present invention, which is excellent.

[0226] Additional Example 1

[0227] At 300°C, the process of injecting the precursor (CpHf) into the Si substrate, injecting the activator (HI), and reacting with the reactant (O3) was repeated to obtain a film of about 13nm. The secondary ion mass spectrometry (SIMS) analysis method uses ion sputtering to dig into the film along the axial direction, and considers the C impurity content (counts) when the sputtering time (sputter time) is 50 seconds with less contamination on the surface layer of the substrate, such as Figure 2 As shown, it was confirmed that the C impurity value was about 700 counts / second.

[0228] Additional Comparative Example 1

[0229] At 300°C, the process of injecting the precursor (CpHf) into the Si substrate and reacting with the reactant (O3) was repeated to obtain a thin film of about 13 nm.

[0230] The secondary ion mass spectrometry (SIMS) analysis method uses ion sputtering to dig into the film along the axial direction, and considers the C impurity content (counts) when the sputtering time is 50 seconds, which is located at the surface layer of the substrate with less contamination. Figure 3 As shown, it was confirmed that the C impurity value was about 1100 counts / second.

[0231] Therefore, it can be confirmed that when the predetermined compound is used as the dielectric film activator of the present invention, the thickness, deposition rate increase rate, density, and dielectric properties of the dielectric film can all be improved, and the impurity reduction property is also excellent, so the dielectric film can be effectively formed even on a substrate with a complex pattern.

Claims

1. A dielectric film activator, wherein: The second ligand contained in the dielectric film activator is used to replace the first ligand directly connected to the central metal of the precursor adsorbed on the substrate to provide an activated substrate-adsorbed precursor.

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

3. The dielectric film activator according to claim 1, wherein The molecule of the precursor adsorbed on the substrate is selected from the structure represented by the following chemical formula 1 and the structure represented by the following chemical formula 2. [Chemical formula 1] 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, R'1 to R'3 are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, [Chemical formula 2] 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.

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

5. The dielectric film activator according to claim 1, wherein The first ligand is the ligand of the chemical formula 1 or 2, the ligand of the precursor adsorbed on the substrate further comprises one or more selected from chlorine, fluorine and bromine, and the dielectric film activator comprises one or more halogen selected from iodine and bromine.

6. The dielectric film activator according to claim 1, wherein The dielectric film activator is hydrogen iodide, hydrogen bromide, or a mixed gas in which hydrogen iodide or hydrogen bromide is mixed with an inert gas at a molar fraction of 1 to 99.

7. The dielectric film activator according to claim 1, wherein The activated substrate adsorbs the precursor, which promotes the reaction with the reaction gas injected before or after the precursor, and reduces the residual carbon compound impurity content.

8. The dielectric film activator according to claim 7, wherein The reduction in the above residual carbon compound impurity content includes: Reduction of the impurity content of by-product carbon-oxygen compounds generated by the combination of the precursor desorption ligand and the reactants; and Reduction in the impurity content of carbon compounds that are not desorbed from the precursor.

9. The dielectric film activator according to claim 8, wherein The reduction in the content of the non-desorbed carbon compound impurities is caused by replacing the ligand of the precursor adsorbed on the substrate with the dielectric film activator contained in the dielectric film activator.

10. The dielectric film activator according to claim 1, wherein The adsorption state of the precursor before replacing the above ligand is represented by the following chemical formula 3-1, and the adsorption state of the precursor after replacing the above ligand is represented by the following chemical formula 3-2, [Chemical formula 3-1] Substrate-MX n In the above Chemical Formula 3-1, M is Hf or Zr, n is an integer of 1 to 4, X is the ligand type of Chemical Formula 1, the ligand type of Chemical Formula 2, F or Cl and they are different from each other, [Chemical formula 3-2] Substrate-MY m 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. The dielectric film activator according to claim 1, wherein The substrate is a silicon wafer, an insulating film or a dielectric film containing -H or -OH terminal groups.

12. The dielectric film activator according to claim 1, wherein The dielectric film is a deposited film, wherein the deposition includes atomic layer deposition, plasma enhanced atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition, organometallic chemical vapor deposition or low pressure chemical vapor deposition.

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

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

15. The semiconductor substrate according to claim 13, wherein The film density of the above dielectric film is 9.5 g / cm 3 In the above, the carbon impurities measured by secondary ion mass spectrometry were 1000 counts / second or less, and the iodine atoms measured by secondary ion mass spectrometry were 50 counts / second or more.

16. A semiconductor device, wherein: Comprising the semiconductor substrate according to claim 13.

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