Metal complex

Abstract

To provide a complex capable of forming a film with low impurity content when used as a precursor compound for ALD.SOLUTION: The present invention provides a precursor complex for forming a metal thin film, the precursor complex having a central metal and a ligand that is coordinated to the central metal, wherein (i) the central metal has an atomic polarizability of 45 to 51 and satisfies the following conditions: polarization volume≤200 and relative dielectric constant≤2.20, or (ii) the central metal has an atomic polarizability of 52 to 90 and satisfies the following conditions: polarization volume≤240 and relative dielectric constant≤2.50.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to metal complexes. [Background technology]

[0002] Atomic layer deposition (hereinafter, also referred to as "ALD") is known as a method for forming films on various substrates, and various metal compounds are used as raw material compounds. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-36068 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a complex that, when used to form a metal film, can form a film with a low impurity content. [Means for solving the problem]

[0005] The present disclosure includes the following aspects. [Section 1] having a central metal and a ligand coordinated to the central metal, The central metal has an atomic polarizability of 45 to 51; The following conditions: Polarization volume ≦200 Dielectric constant≦2.20 A raw material complex for forming thin metal films that satisfies the above requirements. [Section 2] having a central metal and a ligand coordinated to the central metal, The central metal has an atomic polarizability of 52 to 90; The following conditions: Polarization volume ≦240 Dielectric constant≦2.50 A raw material complex for forming thin metal films that satisfies the above requirements. [Section 3] Surface charge density Surface charge density is 0.007e / Å 2 The area above is 10% or less of the entire area of ​​the complex molecule, or the surface charge density is -0.007e / Å 2 Item 3. A raw material complex for forming a metal thin film according to Item 1 or 2, wherein the area below is 10% or less of the entire area of ​​the complex molecule. [Section 4] 4. The metal thin film-forming raw material complex according to any one of items 1 to 3, wherein the ligand is a monodentate ligand, a polydentate ligand, or both of these ligands. [Section 5] 5. The metal thin film-forming raw material complex according to any one of items 1 to 4, wherein the Pauling electronegativity of an atom in the ligand that is coordinately bonded to the metal is 3.1 or less. [Section 6] 6. The raw material complex for forming a metal thin film according to any one of items 1 to 5, wherein the ligand has at least one branched alkyl group having 3 or more carbon atoms. [Section 7] 7. The raw material complex for forming a metal thin film according to any one of items 4 to 6, wherein the monodentate ligand is a carbonyl, an alkyne, an alkyl, a fluoroalkyl, an allyl, an aminoalkyl, a hydride, or an alkylsilane. [Section 8] Item 7. The metal thin film-forming raw material complex according to any one of Items 4 to 6, wherein the polydentate ligand is a bidentate ligand, and the bidentate ligand is an alkyldiene, a cyclopentadiene, an acetylacetonate, an alkyldiamine, or an alkyldisilane. [Section 9] 7. The metal thin film-forming raw material complex according to any one of items 4 to 6, wherein the polydentate ligand is a tridentate ligand, and the tridentate ligand is an amidinate. [Section 10] 10. The raw material complex for forming a metal thin film according to any one of items 1 to 9, wherein the central metal has an oxidation number of 1 or more. [Section 11] 11. The metal thin film forming raw material complex according to any one of items 1 and 3 to 10, wherein the central metal is cobalt, nickel or copper. [Section 12] Item 12. The complex for forming a metal thin film according to any one of items 1 and 3 to 11, wherein the complex has a vapor pressure of 6.0 Torr or more at 100° C. [Section 13] Item 13. The complex for forming a metal thin film according to any one of items 1 and 3 to 12, wherein the central metal is cobalt and the vapor pressure at 100° C. is 6.0 Torr or more. [Section 14] Item 14. The complex for forming a metal thin film according to any one of items 1 and 3 to 13, wherein the central metal is nickel and the vapor pressure at 100° C. is 6.3 Torr or more. [Section 15] 15. The complex for forming a metal thin film according to any one of items 1 and 3 to 14, wherein the central metal is copper and the vapor pressure at 100° C. is 6.7 Torr or more. [Section 16] 11. The metal thin film forming raw material complex according to any one of items 2 to 10, wherein the central metal is molybdenum, ruthenium, or tungsten. [Section 17] Item 17. The complex for forming a metal thin film according to any one of items 2 to 10 and 16, wherein the complex has a vapor pressure of 0.6 Torr or more at 100° C. [Section 18] 18. The complex for forming a metal thin film according to any one of items 2 to 10 and items 16 to 17, wherein the central metal is molybdenum and the vapor pressure at 100° C. is 0.6 Torr or more. [Section 19] 19. The complex for forming a metal thin film according to any one of items 2 to 10 and 16 to 18, wherein the central metal is ruthenium and the vapor pressure at 100° C. is 2.8 Torr or more. [Section 20] 20. The complex for forming a metal thin film according to any one of items 2 to 10 and 16 to 19, wherein the central metal is tungsten and has a vapor pressure at 100° C. of 3.6 Torr or more. [Section 21] 21. The complex for forming a metal thin film according to any one of items 1 to 20, which is used in an atomic layer deposition method. [Section 22] 22. An atomic layer deposition method, comprising using the complex according to any one of items 1 to 21 as a raw material compound. [Section 23] Item 23. The atomic layer deposition method according to item 22, wherein a film formation temperature during film formation using the complex according to any one of items 1 to 21 is 200° C. or lower. [Section 24] Item 24. The atomic layer deposition method according to item 22 or 23, for use in producing a semiconductor substrate. [Section 25] 1. A method for selecting a precursor complex for use in atomic layer deposition, comprising the steps of: The atomic polarizability of the central metal is 45-51, Polarization volume is 200 or less, Dielectric constant is 2.20 or less, Surface charge density is 0.007e / Å 2 The area above this is 10% or less of the entire molecule, or the surface charge density is -0.007e / Å 2 The area of ​​the following molecules is less than 10% of the whole molecule. and selecting a complex wherein [Section 26] 1. A method for selecting a precursor complex for use in atomic layer deposition, comprising the steps of: The atomic polarizability of the central metal is 52 to 90. Polarization volume is 220 or less, Dielectric constant is 2.50 or less, Surface charge density is 0.007e / Å 2 The area above this is 10% or less of the entire molecule, or the surface charge density is -0.007e / Å 2 The area of ​​the following molecules is less than 10% of the whole molecule. and selecting a complex wherein [Section 27] Item 26. The method according to item 25, wherein the vapor pressure is 1.0 Torr or more at 100°C. [Section 28] Item 28. The method according to item 25 or 27, wherein the central metal of the complex is cobalt, nickel, or copper. [Section 29] Item 27. The method according to item 26, wherein the vapor pressure is 0.6 Torr or more at 100°C. [Section 30] 30. The method according to item 26 or 29, wherein the central metal of the complex is molybdenum, ruthenium, or tungsten. [Section 31] Item 31. The method according to any one of Items 25 to 30, wherein the polarization volume, the relative dielectric constant, the surface charge density and the vapor pressure of the complex are determined by simulation. [Section 32] Item 32. The method according to Item 31, wherein the simulation is at least one of a COSMO-SAC method, a DFT method, and an AMS method. [Section 33] Item 33. The method according to Item 32, wherein the COSMO-SAC method in the simulation is a modified COSMO-SAC method. Effect of the Invention

[0006] Since the complexes of the present disclosure have a high vapor pressure, when they are used as raw materials for ALD, they can be vaporized at low temperatures and decomposition due to heat is suppressed. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing an example of a film formation apparatus for carrying out the atomic layer deposition method of the present disclosure. [Diagram 2] FIG. 2 is a graph plotting the calculated values ​​(Rev. 3) calculated by the calculation method of the present invention and the calculated values ​​calculated by the existing COSMO-SAC method. [Diagram 3] FIG. 3 is a table showing the calculation values ​​(Rev. 3) calculated by the calculation method of the present invention and the calculation values ​​calculated by the existing COSMO-SAC method. [Figure 4] FIG. 4 shows the results of TG-DTA analysis of the compound of Example 1. [Diagram 5] FIG. 5 is a graph showing a comparison between the calculated and measured vapor pressures of the compound of Example 1. [Figure 6] FIG. 6 shows the results of TG-DTA analysis of the compound of Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present disclosure will be described below. However, the following description is intended to embody the technical ideas of the present disclosure, and unless otherwise specified, the invention is not limited to the following.

[0009] (Complex) The complexes of the present disclosure are having a central metal and a ligand coordinated to the central metal, (i) the central metal has an atomic polarizability of 45 to 51; The following conditions: Polarization volume ≦200 Dielectric constant≦2.20 or (ii) having a central metal and a ligand coordinated to the central metal; The central metal has an atomic polarizability of 52 to 90; The following conditions: Polarization volume ≦240 Dielectric constant≦2.50 Meet the following.

[0010] In ALD, typically, a raw material compound is vaporized in an evaporator, and the gaseous raw material compound is introduced into a film-forming chamber, where it is deposited on a substrate to form a film of the raw material compound. The film of the raw material compound is reduced to form, for example, a metal film. That is, in ALD, the raw material compound is first vaporized, and at this time, heating is generally performed. However, if the heating temperature is high, the complex is decomposed, and the decomposition product may be mixed into the film as an impurity.

[0011] On the other hand, the complex of the present disclosure that satisfies the above conditions has a high vapor pressure. Therefore, the complex of the present disclosure can be vaporized at a relatively low temperature. As a result, decomposition of the complex is suppressed, and the incorporation of impurities into the film is suppressed.

[0012] (i) When the atomic polarizability of the central metal is 45 to 51 The complexes of the present disclosure are It has a polarization volume of 200 or less, for example, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 125 or less, or 120 or less. The lower limit of the polarization volume of the complex of the present disclosure is not particularly limited, and may be, for example, 10 or more, 30 or more, 50 or more, 60 or more, 70 or more, or 80 or more.

[0013] The complex of the present disclosure has a relative dielectric constant of 2.20 or less, for example, 2.10 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, or 1.60 or less. The lower limit of the relative dielectric constant of the complex of the present disclosure is not particularly limited, and may be, for example, 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, or 1.50 or more.

[0014] In one embodiment, the complex of the present disclosure in case (i) is: The following conditions: Polarization volume≦180 and relative dielectric constant≦2.00, Polarization volume ≦170 and relative dielectric constant ≦1.90, Polarization volume ≦160 and relative dielectric constant ≦1.80 Polarization volume ≦125 and relative dielectric constant ≦2.20 Polarization volume ≦ 120 and relative dielectric constant ≦ 2.20, or Polarization volume ≦120 and relative dielectric constant ≦2.00 can be satisfied.

[0015] (ii) The atomic polarizability of the central metal is 52 to 90. The complexes of the present disclosure are The complex has a polarization volume of 240 or less, for example, 234 or less, 230 or less, 220 or less, 210 or less, 200 or less, 190 or less, or 180 or less. The lower limit of the polarization volume of the complex of the present disclosure is not particularly limited, and may be, for example, 10 or more, 30 or more, 50 or more, 60 or more, 70 or more, or 80 or more.

[0016] The complex of the present disclosure has a relative dielectric constant of 2.50 or less, for example, 2.40 or less, 2.36 or less, 2.30 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, or 1.60 or less. The lower limit of the relative dielectric constant of the complex of the present disclosure is not particularly limited, and may be, for example, 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, or 1.50 or more.

[0017] In one embodiment, the complex of the present disclosure in case (ii) is: The following conditions: Polarization volume ≦220 and relative dielectric constant ≦2.50, Polarization volume ≦234 and relative dielectric constant ≦2.36, Polarization volume ≦200 and relative dielectric constant ≦2.40, or Polarization volume ≦180 and relative dielectric constant ≦2.30 can be satisfied.

[0018] The complexes of the present disclosure having a polarization volume and a relative dielectric constant within the above ranges have a high vapor pressure and can be vaporized at a relatively low temperature.

[0019] In one embodiment, the surface charge density of the complex is preferably less than 0.007 e / Å 2 The above area is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and further preferably 3% or less.

[0020] In one embodiment, the surface charge density of the complex is preferably −0.007 e / Å 2 The area below is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less.

[0021] In one embodiment, the surface charge density of the complex is preferably less than 0.007 e / Å 2 The above area is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less, and is preferably -0.007e / Å 2 The area below is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less.

[0022] Here, the area of ​​the entire molecule is the surface area when expressed as a collection of atoms having the atomic radius used in the COSMO-SAC method described below.

[0023] The polarization volume, the relative dielectric constant, the surface charge density, and the vapor pressure can be measured by simulation.

[0024] Examples of the above simulation include the COSMO-SAC (Conductor-like Screening Model-Segment Activity Coefficient) method, the DFT (Density Functional Theory) method, and the AMS (Amsterdam Modeling Suite) method.

[0025] Although the COSMO-SAC method is generally applied to calculate vapor pressure, it is difficult to predict the vapor pressure of the metal complex related to this invention with high accuracy. Therefore, in this invention, the accuracy of predicting the vapor pressure of metal complexes is improved by adding the following procedure to the COSMO-SAC method. This simulation method with improved vapor pressure prediction accuracy is hereinafter referred to as the "improved COSMO-SAC method." Details of the method for improving prediction accuracy are described in "Study on Predicting the Vapor Pressure of Metal Complexes by the COSMO-SAC Method" (Noboru Sato et al., Society of Chemical Engineers, 53rd Autumn Meeting), but the main points are explained below.

[0026] More specifically, in the calculation of vapor pressure in the present invention, the molecular activity coefficient due to dispersion forces γ dsp When calculating, the empirical parameters (ε dsp ) is used, where ε dsp and the polarizability α of the metal atom M There is a correlation between the two, and the correlation formula is: ε dsp =1035×α M 1.34 From this correlation equation, the unknown ε dspThe polarizability of the metal atom changes depending on the functional group to which it is bonded, so it is calculated for each complex. The polarizability of the central metal, α, can be calculated by subtracting the polarizability of the ligand from the polarizability of the complex molecule. M (see below). TIFF2025031687000001.tif44156

[0027] Molecular polarizability α Mol and γ dsp There is a correlation between these two, as shown in the following correlation formula: It is expressed as TIFF2025031687000002.tif10170. From the above correlation formula, -T In(γ dsp If the value of P COSMO is an overestimated or underestimated value from the actual value by the difference (ΔE). COSMO This error can be corrected by multiplying it by exp(ΔE / RT), and a more accurate steam P COSMO * P COSMO * =P COSMO It can be calculated by ×exp(ΔE / RT).

[0028] In the COSMO-SAC method, the vapor pressure of complexes containing tertiary carbon, quaternary carbon, and tertiary nitrogen is underestimated. This is thought to be due to an overestimation of the dispersion force due to the surfaces of these branched atoms. Therefore, the surface area of ​​the tertiary atoms is converted to 1 / 2 and the surface area of ​​the quaternary atoms is converted to 0, and the molecular activity coefficient γ dsp * Calculate the vapor pressure P COSMO * For γ dsp * / γ dsp By applying this, the actual vapor pressure can be reproduced.

[0029] The results of comparing the predicted vapor pressures of metal complexes with the reported values ​​are shown in Figures 2 and 3. Note that the predicted values ​​shown are both values ​​calculated using the "improved COSMO-SAC method" described above and values ​​calculated using the existing COSMO-SAC method. The calculated values ​​of the present invention predict vapor pressures with higher accuracy than those calculated using the existing method.

[0030] The DFT method is applied to the polarization volume, dielectric constant, and surface charge density. For the prediction of the polarization volume, Gaussian09W is used, and measurements are performed at the B3LYP / 6-311+G(d, p) level. For the prediction of the dielectric constant, AMS (Amsterdam Modeling Suite) is used to predict the density of the metal complex in the liquid phase, which is necessary for the prediction, and the dielectric constant is predicted from the Clausius-Mossotti relational equation from the polarizability and density in the liquid phase. For the prediction of the surface charge density, AMS (Amsterdam Modeling Suite) is used, and measurements are performed at the BP86 / TZP level.

[0031] The complexes of the present disclosure are preferably organometallic compounds, which are comprised of a metal atom and a ligand, particularly a monodentate and / or polydentate ligand, coordinated to the metal atom.

[0032] Examples of the monodentate ligand include halogen, hydride, alkyl, alkenyl, cycloalkyl, aryl, alkynyl, alkylimino, amine, dialkylaminoalkyl, monoalkylamino, dialkylamino, alkoxy, alkoxyalkyl, hydrazide, phosphide, nitrile, silyl, and carbonyl.

[0033] Examples of bidentate ligands that are polydentate ligands include diamine, di(silyl-alkyl)amino, di(alkyl-silyl)amino, disilylamino, dialkylaminoalkoxy, alkoxyalkyldialkylamino, siloxy, diketonate, cyclopentadienyl, pyrazolate, ketoiminate, and diketiminate.

[0034] Examples of polydentate ligands, that is, tridentate or higher ligands, include amidinates, guanidinates, phosphoguanidinates, phosphoamidinates, and the like.

[0035] The ligand has a Pauling electronegativity of 3.1 or less for the atom that coordinates to the metal, and may be preferably a monodentate, bidentate, or tridentate ligand.

[0036] The ligand may be, preferably as a monodentate ligand, a carbonyl, an alkyne, an alkylamine, a hydride.

[0037] The ligand may preferably be an alkyl diene, a cyclopentadiene, an acetylcetonate as a bidentate ligand.

[0038] The ligand may preferably be an amidinate as a tridentate ligand.

[0039] (i) When the atomic polarizability of the central metal is 45 to 51 The central metal of the complexes of the present disclosure may preferably be cobalt, nickel, or copper, more preferably cobalt.

[0040] (ii) The atomic polarizability of the central metal is 52 to 90. The central metal of the complexes of the present disclosure may preferably be molybdenum, ruthenium, or tungsten, more preferably ruthenium or tungsten.

[0041] By having the above central metal, the complexes of the present disclosure may have a higher vapor pressure.

[0042] (i) When the atomic polarizability of the central metal is 45 to 51 The vapor pressure of the complex of the present disclosure at 100° C. is preferably 1.0 Torr or more, more preferably 2.0 Torr or more, and even more preferably 3.0 Torr or more, for example, 3.5 Torr or more, 4.5 Torr or more, 5.5 Torr or more, 6.0 Torr or more, 6.3 Torr or more, or 6.7 Torr or more. The upper limit of the vapor pressure of the complex of the present disclosure at 100° C. is not particularly limited, and may be, for example, 55 Torr or less, 50 Torr or less, 45 Torr or less, 40 Torr or less, 35 Torr or less, 30 Torr or less, 25 Torr or less, 20 Torr or less, 15 Torr or less, 10 Torr or less, 8 Torr or less, 7 Torr or less, or 6 Torr or less.

[0043] In a preferred embodiment, The central metal is cobalt, and the vapor pressure at 100°C is 6.0 Torr or more. The central metal is nickel and has a vapor pressure of 6.3 Torr or more at 100°C; or The central metal is copper, and its vapor pressure at 100° C. is 6.7 Torr or more.

[0044] (ii) The atomic polarizability of the central metal is 52 to 90. The vapor pressure of the complex of the present disclosure at 100° C. may be preferably 0.6 Torr or more, more preferably 1.0 Torr or more, even more preferably 2.0 Torr or more, and even more preferably 2.8 Torr or more, for example, 3.0 Torr or more, 3.5 Torr or more, 3.6 Torr or more, 4.5 Torr or more, or 5.5 Torr or more. The upper limit of the vapor pressure of the complex of the present disclosure at 100° C. is not particularly limited, and may be, for example, 10 Torr or less, 8 Torr or less, 7 Torr or less, or 6 Torr or less.

[0045] In a preferred embodiment, The central metal is molybdenum, and the vapor pressure at 100°C is 0.6 Torr or more. the central metal is ruthenium and has a vapor pressure of 2.8 Torr or more at 100°C; or The central metal is tungsten, and its vapor pressure at 100° C. is 3.6 Torr or more.

[0046] By having a vapor pressure in the above range, vaporization at a low temperature is possible, and decomposition of the complex is suppressed, which in turn makes it possible to suppress the incorporation of impurities into the film in ALD using the complex of the present disclosure as a raw material.

[0047] The vapor pressure of the complex of the present disclosure can be measured by introducing the complex into a bottle equipped with a pressure system and measuring the pressure at each given temperature.

[0048] In the complex of the present disclosure, when the ligand contains an alkyl group having 3 or more carbon atoms, the alkyl group may preferably have a branched carbon. That is, the complex of the present disclosure may have at least one branched chain alkyl group having 3 or more carbon atoms.

[0049] Examples of the complexes of the present disclosure include the following complexes: TIFF2025031687000003.tif33170

[0050] The complexes of the present disclosure can be used in a variety of applications, such as atomic layer deposition, chemical vapor deposition, catalytic applications (e.g., catalysts for hydrogen fuel cells, catalysts for hydrogen evolution reactions), cathode electrodes in lithium ion batteries, anodes in batteries, photodetectors, biosensing, high performance thermoelectric materials, and catalysts.

[0051] Currently, many chemical growth methods, such as CVD and atomic layer deposition (ALD), using metal complexes are used in semiconductor manufacturing processes. The film types are diverse, including metal films, metal nitrides, metal oxides, and metal carbides, and are being widely investigated in the following processes. High dielectric constant gate insulating film: HfOx, HfLaOx, etc. Gate cap film: TiAlOx, etc. Capacitor insulating film (DRAM): ZrOx, AlOx, HfOx, etc. Block oxide film (Flash Memory): AlOx, etc. Metal gate electrode (including work function metal): W, TiN, TaN, TiAlC, TiAlN, etc. Wiring materials (including barrier metal, liner metal, seed metal, and metal cap): Cu, Co, Ru, Mo, TaN, TiN, MoN, WC, etc. Via hole and contact hole filling materials (including adhesion layers): W, Mo, Co, Ru, TiN, MoN, WC, etc. Metal hard mask (including sidewall spacer): TiN, TiOx, etc. Etching stop layer: AlO, AlNO, etc. Metal film (wiring material, embedding material) selective growth promotion material: Pd, etc. High thermal conductivity insulating film: AlN, etc. Furthermore, in the atomic layer etching (ALE) process, metal complexes are sometimes used to etch difficult-to-etch materials such as high-k insulating films.

[0052] (Atomic layer deposition method) The present disclosure provides an atomic layer deposition method using the above-described complex of the present disclosure as a raw material compound.

[0053] The complex of the present disclosure has a high vapor pressure and can therefore be vaporized at a relatively low temperature, for example, at or below 200° C. This prevents the complex, which is a raw material compound, from being decomposed, and prevents impurities from being mixed into the thin film to be formed.

[0054] The atomic layer deposition method of the present disclosure is performed, for example, by a film formation apparatus as shown in FIG. 1. In the film formation chamber 1, a deposition process is performed in which a raw material compound vaporized in a raw material container 2 is deposited on a substrate prepared in advance, and the raw material compound is deposited on the substrate. Thereafter, in the film formation chamber 1, a film formation process is performed in which a thin film is formed by reduction with a reducing gas, and a thin film is formed. Note that, although there is only one raw material container 2 in FIG. 1, there may be two or more raw material containers, for example, when two or more kinds of raw material compounds are used. The film formation apparatus will be specifically described below.

[0055] In the source container 2, the source liquid 25 containing the source compound is heated and vaporized as necessary. The vaporized source compound is carried to the film formation chamber 1 by an inert carrier gas. The source container 2 may be heated to, for example, 30°C or higher, 45°C or higher, 200°C or lower, or 120°C or lower in order to vaporize the source liquid. The source compound may be heated to 45°C to 120°C, or 30°C to 200°C.

[0056] The inert carrier gas is, for example, nitrogen, argon, or helium. The flow rate of the inert carrier gas is adjusted by a mass flow controller (hereinafter, also referred to as "MFC") 3. The pressure inside the source container 2 is adjusted by a needle valve 4. The flow rate of the inert carrier gas is, for example, 10 sccm to 100 sccm. The pressure inside the source container 2 is measured by a pressure gauge 26. The pressure value is, for example, 10 Torr to 100 Torr.

[0057] The source material container 2 is connected to a supply line 5 leading to the film formation chamber 1, and a line branching into an exhaust line 6. The supply line 5 and the exhaust line 6 have valves 7 and 8, respectively, and the supply and exhaust of source material are switched by opening and closing the valves 7 and 8. The supply line 5 and the exhaust line 6 may have a heating mechanism. The heating mechanism may be a heater arranged around the piping, typically a jacket heater.

[0058] The supply line 5 and exhaust line 6 can be purged with an inert purge gas. The inert purge gas is, for example, nitrogen, argon, or helium. The flow rate of the inert purge gas is adjusted by an MFC 9. The flow rate of the inert purge gas is, for example, 10 sccm to 100 sccm. The purge destination is switched to the supply line 5 or the exhaust line 6 by opening and closing valves 10 and 11. A sequence is set so that when the raw material compound flows through the supply line 5, the inert purge gas flows into the exhaust line 6, and when the raw material compound flows through the exhaust line 6, the inert purge gas flows into the supply line 5.

[0059] When the reaction gas is a high-pressure gas such as hydrogen or oxygen, the flow rate is adjusted by the MFC 12 and the reaction gas is supplied. The flow rate is, for example, 10 sccm to 1000 sccm. When the reaction gas is a liquid at room temperature and normal pressure such as water or formic acid, the reaction gas is supplied using an inert carrier gas in the same manner as the raw material compound.

[0060] The supply line for the reactive gas branches into a supply line 13 connected to the film formation chamber 1, and an exhaust line 14. The supply line 13 and the exhaust line 14 have valves 15 and 16, respectively, and the supply and exhaust of the reducing gas are switched by opening and closing the valves 15 and 16. The supply line 13 and the exhaust line 14 may have a heating mechanism. The heating mechanism may be a heater arranged around the piping, typically a jacket heater.

[0061] The supply line 13 and exhaust line 14 can be purged with an inert purge gas. The inert purge gas is, for example, nitrogen, argon, or helium. The flow rate of the inert purge gas is adjusted by the MFC 17. The flow rate of the inert purge gas is, for example, 10 sccm to 100 sccm. The purge destination is switched to the supply line 13 or the exhaust line 14 by opening and closing the valves 18 and 19. A sequence is set so that when the reaction gas flows through the supply line 13, the inert purge gas flows into the exhaust line 14, and when the reaction gas flows through the exhaust line 14, the inert purge gas flows into the supply line 13.

[0062] An inert balance gas line for adjusting the flow rate may be connected to the film formation chamber 1. The inert balance gas is, for example, nitrogen, argon, or helium. The flow rate of the inert balance gas is adjusted by the MFC 20. The flow rate of the inert balance gas is, for example, 10 sccm to 100 sccm.

[0063] The film formation chamber 1 includes a film formation table 21. Before the introduction of the raw material compound, the second main surface of the substrate on which the film is to be formed is usually brought into contact with the film formation table 21. The second main surface of the substrate is the surface opposite to the first main surface.

[0064] In the film formation chamber 1, a source compound vaporized in a source container 2 is introduced. That is, the vaporized source compound comes into contact with the first main surface of the substrate, and a deposition process is performed in which the vaporized source compound is deposited on the substrate.

[0065] In the film formation chamber 1, after the deposition process, a film formation process is carried out in which the deposit is reacted with a reactive gas to form a thin film.

[0066] The film formation chamber 1 may be equipped with a heating mechanism, and is heated to, for example, 100°C to 300°C.

[0067] The film formation chamber 1 has an exhaust line 22 for exhausting gas. The exhaust line 22 exhausts raw material compounds, carrier gas, reducing gas, etc. remaining in the film formation chamber 1. Examples of the exhaust method include a method of purging the system with an inert gas such as nitrogen or argon, a method of exhausting by reducing the pressure in the system, a combination of these, etc.

[0068] The exhaust line 22 includes a butterfly valve 23 for adjusting the pressure in the film formation chamber 1. The pressure in the film formation chamber 1 is adjusted by the opening degree of the butterfly valve 23, and the pressure in the film formation chamber 1 is, for example, 10 Torr to 30 Torr.

[0069] The exhaust line 22 is connected to the exhaust line 6 and the exhaust line 14 downstream of the butterfly valve 23 (i.e., in the opposite direction to the film formation chamber 1). The exhaust line 22 has a pump 24 downstream of the connection points with the exhaust line 6 and the exhaust line 14.

[0070] As described above, the source liquid 25 containing the source compound is present in the source container 2, and the source compound vaporized in the source container 2 is transferred by the carrier gas through the supply line 5 to the film formation chamber 1. In the film formation chamber 1, the source compound vaporized in the source container 2 is deposited on a substrate prepared in advance. Thereafter, in the film formation chamber 1, a thin film is formed by reacting with a reactive gas. This process is repeated a specified number of times to obtain a thin film with a desired thickness.

[0071] The above-mentioned substrate is usually placed on a film formation stage provided in the film formation chamber 1 before the raw material compounds are introduced.

[0072] The material constituting the substrate is not particularly limited, but examples thereof include metals such as copper, silver, gold, platinum, nickel, palladium, and aluminum; silicon; ceramics such as indium arsenide, indium gallium arsenide, silicon oxide, silicon nitride, silicon carbide, titanium nitride, tantalum oxide, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, and gallium nitride; and glass.

[0073] In one embodiment, the material constituting the substrate is copper, silver, gold, platinum, nickel, palladium, or aluminum, and is preferably copper.

[0074] The shape of the substrate is not particularly limited, and may be plate-like, rod-like, spherical, layer-like, fibrous, scale-like, or the like.

[0075] In one embodiment, the base material may be in the form of a layer provided on a substrate, for example, wiring on a wiring board.

[0076] The temperature of the substrate when the raw material compound is deposited on the substrate can be, for example, 20 to 300°C, preferably 50 to 200°C, more preferably 80 to 180°C, and further preferably 100 to 160°C.

[0077] According to the atomic layer deposition method of the present disclosure, it is possible to form a thin film with little impurity mixing, and therefore the atomic layer deposition method of the present disclosure can be suitably used for, for example, manufacturing a semiconductor substrate.

[0078] (Method of selecting a raw material complex for use in atomic layer deposition) The present disclosure provides a method for selecting a precursor complex for use in atomic layer deposition, the method comprising the steps of: (i) The atomic polarizability of the central metal is 45 to 51; Polarization volume is 200 or less, Dielectric constant is 2.20 or less, Surface charge density is 0.007e / Å 2 Complexes with an area of ​​10% or less of the total molecular area or a surface charge density of -0.007e / Å 2The area of ​​the following molecules is less than 10% of the total area of ​​the molecule. or by selecting a complex where (ii) the atomic polarizability of the central metal is 52 to 90; Polarization volume is 220 or less, Dielectric constant is 2.50 or less, Surface charge density is 0.007e / Å 2 The area above this is 10% or less of the total area of ​​the molecule, or the surface charge density is -0.007e / Å 2 The area of ​​the following molecules is less than 10% of the total area of ​​the molecule. Selecting a complex in which The present invention provides a method comprising:

[0079] According to the method for selecting a complex of the present disclosure, a complex having a high vapor pressure can be found.

[0080] (i) When the atomic polarizability of the central metal is 45 to 51 In the method of selecting a complex of the present disclosure, a complex is selected whose polarization volume is 200 or less, for example, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 125 or less, or 120 or less. Also, a complex is selected whose polarization volume is, for example, 10 or more, 30 or more, 50 or more, 60 or more, 70 or more, or 80 or more.

[0081] In the method for selecting a complex of the present disclosure, a complex having a dielectric constant of 2.20 or less, for example, 2.10 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, or 1.60 or less is selected. Also, a complex having a dielectric constant of, for example, 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, or 1.50 or more is selected.

[0082] (ii) the atomic polarizability of the central metal is 52 to 90; In the method for selecting a complex of the present disclosure, a complex is selected whose polarization volume is 240 or less, for example, 234 or less, 230 or less, 220 or less, 210 or less, 200 or less, 190 or less, or 180 or less. Also, a complex is selected whose polarization volume is, for example, 10 or more, 30 or more, 50 or more, 60 or more, 70 or more, or 80 or more.

[0083] In the method for selecting a complex of the present disclosure, a complex having a dielectric constant of 2.50 or less, for example, 2.40 or less, 2.36 or less, 2.30 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, or 1.60 or less is selected. Also, a complex having a dielectric constant of, for example, 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, or 1.50 or more is selected.

[0084] In the method of selecting a complex according to the present disclosure, the surface charge density is 0.007 e / Å 2 Complexes with an area of ​​10% or less of the total molecular area or a surface charge density of -0.007e / Å 2 Select complexes whose areas below are less than 10% of the area of ​​the entire molecule.

[0085] In one embodiment, the surface charge density of the complex is preferably less than 0.007 e / Å 2 The above area is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and further preferably 3% or less.

[0086] In one embodiment, the surface charge density of the complex is preferably −0.007 e / Å 2 The area below is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less.

[0087] In one embodiment, the surface charge density of the complex is preferably less than 0.007 e / Å 2 The above area is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less, and is preferably -0.007e / Å 2 The area below is 10% or less of the area of ​​the entire molecule, more preferably 5% or less, and even more preferably 3% or less.

[0088] (i) When the atomic polarizability of the central metal is 45 to 51 In the method for selecting a complex of the present disclosure, a complex is selected whose vapor pressure at 100° C. is preferably 1.0 Torr or more, more preferably 2.0 Torr or more, and even more preferably 3.0 Torr or more, for example, 3.5, 4.5 Torr or more, 5.5 Torr or more, 6.0 Torr or more, 6.3 Torr or more, or 6.7 Torr or more. Also, a complex is selected whose vapor pressure at 100° C. is, for example, 55 Torr or less, 50 Torr or less, 45 Torr or less, 40 Torr or less, 35 Torr or less, 30 Torr or less, 25 Torr or less, 20 Torr or less, 15 Torr or less, 10 Torr or less, 8 Torr or less, 7 Torr or less, or 6 Torr or less.

[0089] (ii) When the atomic polarizability of the central metal is 52 to 90 In the method for selecting a complex of the present disclosure, a complex is selected that has a vapor pressure at 100° C. of preferably 0.6 Torr or more, more preferably 1.0 Torr or more, even more preferably 2.0 Torr or more, and even more preferably 2.8 Torr or more, for example, 3.0 Torr or more, 3.5 Torr or more, 3.6 Torr or more, 4.5 Torr or more, or 5.5 Torr or more. In addition, a complex is selected that has a vapor pressure at 100° C. of, for example, 10 Torr or less, 8 Torr or less, 7 Torr or less, or 6 Torr or less.

[0090] Complexes having a polarization volume, dielectric constant, surface charge density, and vapor pressure within the above ranges have a high vapor pressure and can be vaporized at a relatively low temperature.

[0091] In one embodiment, in the method of selecting a complex of the present disclosure: (i) When the atomic polarizability of the central metal is 45 to 51 The following conditions: Polarization volume≦180 and relative dielectric constant≦2.00, Polarization volume ≦170 and relative dielectric constant ≦1.90, Polarization volume ≦160 and relative dielectric constant ≦1.80 Polarization volume ≦125 and relative dielectric constant ≦2.20 Polarization volume ≦ 120 and relative dielectric constant ≦ 2.20, or Polarization volume ≦120 and relative dielectric constant ≦2.00 Select a complex that satisfies the following:

[0092] In one embodiment, in the method of selecting a complex of the present disclosure: (ii) When the atomic polarizability of the central metal is 52 to 90 The following conditions: Polarization volume ≦220 and relative dielectric constant ≦2.50, Polarization volume ≦234 and relative dielectric constant ≦2.36, Polarization volume ≦200 and relative dielectric constant ≦2.40, or Polarization volume ≦180 and relative dielectric constant ≦2.30 Select a complex that satisfies the following:

[0093] The polarization volume and the relative dielectric constant can be determined by simulation.

[0094] Examples of the simulation include the Conductor-like Screening Model-Segment Activity Coefficient (COSMO-SAC) method and the Density Functional Theory (DFT) method. The COSMO-SAC method and the DFT method have the same meanings as those described above.

[0095] In the method for selecting a complex of the present disclosure, a complex is selected in which the central metal is preferably cobalt, ruthenium, tungsten, copper, palladium or molybdenum, more preferably cobalt, ruthenium, tungsten, palladium or molybdenum, even more preferably cobalt, ruthenium or tungsten, and particularly preferably cobalt. In a preferred embodiment, cobalt, nickel or copper is selected as the central metal having an atomic polarizability of 45 to 51. In another preferred embodiment, molybdenum, ruthenium or tungsten is selected as the central metal having an atomic polarizability of 52 to 90. A complex having such a central metal may have a higher vapor pressure. EXAMPLES

[0096] The present disclosure will be described below with reference to examples, but the present disclosure is not limited to the following examples.

[0097] TIFF2025031687000004.tif40170

[0098] Example 1 In a glove box, CpCo(CO)2 (300 mg), NaI (49.35 mg), and dry THF (15 mL) were charged into a 30 mL glass inner cylinder autoclave, and after gentle stirring, a septum cap was attached. The mixture was transferred from the glove box to a draft and added to a syringe. Trifluoromethyltrimethylsilane (600 mg) was gradually added dropwise. The lid of the autoclave was closed, an oil bath was attached, and the mixture was heated and stirred at a bath temperature of 65°C. After 2 hours, heating was stopped. The reaction solution was allowed to cool and concentrated under reduced pressure, and dry hexane (12 mL) was added to the resulting residue. Insoluble matter was removed by filtration through Celite, and the filtrate was concentrated under reduced pressure. 150 mg of a viscous brown liquid was obtained (yield: 36%). The IR and NMR analyses were compared with literature values ​​to confirm that the compound was the target, and TG-DTA analysis was performed. The results are shown in Figure 4.

[0099] In addition, since compounds with high vapor pressure are correlated with the Td50 temperature in TG-DTA, it can be said that complexes with a low Td50 temperature also have a high vapor pressure.

[0100] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0101] [Table 1]

[0102] When the vapor pressure of the above complex was actually measured at 100°C, it was 153 Torr. When the experimental value was compared with the calculated value, it was confirmed that it was within the 99% confidence interval of Rev.3 in Figure 2.

[0103] Example 2 TIFF2025031687000006.tif23170

[0104] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0105] [Table 1]

[0106] Example 3 TIFF2025031687000008.tif24170

[0107] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0108] [Table 2]

[0109] Example 4 TIFF2025031687000010.tif44170

[0110] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0111] [Table 3]

[0112] Example 5 TIFF2025031687000012.tif49170

[0113] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0114] [Table 4]

[0115] Example 6 TIFF2025031687000014.tif33170

[0116] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0117] [Table 5] Example 7 TIFF2025031687000016.tif36170

[0118] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0119] [Table 6] Example 8 TIFF2025031687000018.tif16170

[0120] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0121] [Table 7] Example 9 TIFF2025031687000020.tif20170

[0122] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0123] [Table 8]

[0124] Comparative Example 1 TIFF2025031687000022.tif3250

[0125] The above complex was subjected to TG-DTA analysis, and the results are shown in Figure 6.

[0126] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0127] [Table 9]

[0128] Comparative Example 2 TIFF2025031687000024.tif32170

[0129] The above complex was subjected to TG-DTA analysis.

[0130] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0131] [Table 10]

[0132] Comparative Example 3 TIFF2025031687000026.tif26170

[0133] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0134] [Table 11]

[0135] Comparative Example 4 TIFF2025031687000028.tif35170

[0136] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0137] [Table 12]

[0138] Comparative Example 5 TIFF2025031687000030.tif35170

[0139] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0140] [Table 13]

[0141] Comparative Example 6 Ni(tBu-AMD)2

[0142] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0143] [Table 14]

[0144] Comparative Example 7 Cu(iPr-AMD)2

[0145] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0146] [Table 15]

[0147] Comparative Example 8 Mo(hfac)3

[0148] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0149] [Table 16]

[0150] Comparative Example 9 Mo(Me-AMD)3

[0151] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0152] [Table 17]

[0153] Comparative Example 10 Mo(iPr-AMD)3

[0154] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0155] [Table 18]

[0156] Comparative Example 11 Ru(iPr-AMD)3

[0157] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0158] [Table 19]

[0159] Comparative Example 12 W(iPr-AMD)3

[0160] For the above complexes, the polarization volume, dielectric constant, and surface charge density were calculated by the DFT method, and the vapor pressure was calculated by the modified COSMO-SAC method.

[0161] [Table 20] [Industrial Applicability]

[0162] The complexes disclosed herein can be used to efficiently form high-purity thin films by ALD, and thus the complexes and atomic layer deposition methods disclosed herein can be suitably used in a variety of applications, such as the manufacture of semiconductor substrates. [Explanation of symbols]

[0163] 1... Film formation chamber 2...Raw material container 3, 9, 12, 17, 20…Mass flow controller 4...Needle valve 5, 13…Supply line 6, 14…Exhaust line 7, 8, 10, 11, 15, 16, 18, 19… Valves 21... Film formation table 22…Discharge line 23…Butterfly valve 24…Pump 25…Liquid raw material 26, 27…Pressure gauge

Claims

1. having a central metal and a ligand coordinated to the central metal, the central metal has an atomic polarizability of 45 to 51; The following conditions: Polarization volume≦200 Dielectric constant≦2.20 A raw material complex for forming thin metal films that satisfies the above requirements.

2. having a central metal and a ligand coordinated to the central metal, the central metal has an atomic polarizability of 52 to 90; The following conditions: Polarization volume≦240 Dielectric constant≦2.50 A raw material complex for forming metal thin films that satisfies the above requirements.

3. Surface charge density is 0.007 e / Å ２ The area of ​​the complex is 10% or less of the entire area of ​​the complex molecule, or the surface charge density is -0.007 e / Å ２ 3. The raw material complex for forming a metal thin film according to claim 1, wherein the area below is 10% or less of the area of ​​the entire complex molecule.

4. 3. The metal thin film forming raw material complex according to claim 1, wherein the ligand is a monodentate ligand, a polydentate ligand, or both of these ligands.

5. 3. The metal thin film forming raw material complex according to claim 1, wherein the Pauling electronegativity of an atom in the ligand that is coordinately bonded to the metal is 3.1 or less.

6. 3. The metal thin film forming raw material complex according to claim 1, wherein the ligand has at least one branched alkyl group having 3 or more carbon atoms.

7. 5. The metal thin film forming raw material complex according to claim 4, wherein the monodentate ligand is a carbonyl, an alkyne, an alkyl, a fluoroalkyl, an allyl, an aminoalkyl, a hydride, or an alkylsilane.

8. 5. The metal thin film forming raw material complex according to claim 4, wherein the polydentate ligand is a bidentate ligand, and the bidentate ligand is an alkyldiene, a cyclopentadiene, an acetylacetonate, an alkyldiamine, or an alkyldisilane.

9. 5. The metal thin film-forming raw material complex according to claim 4, wherein the polydentate ligand is a tridentate ligand, and the tridentate ligand is an amidinate.

10. 3. The metal thin film forming raw material complex according to claim 1, wherein the central metal has an oxidation number of 1 or more.

11. 2. The metal thin film forming raw material complex according to claim 1, wherein the central metal is cobalt, nickel or copper.

12. 2. The complex for forming a metal thin film according to claim 1, which has a vapor pressure of 6.0 Torr or more at 100°C.

13. 2. The complex for forming a metal thin film according to claim 1, wherein the central metal is cobalt and the vapor pressure at 100° C. is 6.0 Torr or more.

14. 2. The complex for forming a metal thin film according to claim 1, wherein the central metal is nickel and the vapor pressure at 100° C. is 6.3 Torr or more.

15. 2. The complex for forming a metal thin film according to claim 1, wherein the central metal is copper and the vapor pressure at 100° C. is 6.7 Torr or more.

16. 3. The metal thin film forming raw material complex according to claim 2, wherein the central metal is molybdenum, ruthenium, or tungsten.

17. 3. The complex for forming a metal thin film according to claim 2, which has a vapor pressure of 0.6 Torr or more at 100°C.

18. 3. The complex for forming a metal thin film according to claim 2, wherein the central metal is molybdenum and the vapor pressure at 100° C. is 0.6 Torr or more.

19. 3. The complex for forming a metal thin film according to claim 2, wherein the central metal is ruthenium and the vapor pressure at 100° C. is 2.8 Torr or more.

20. 3. The complex for forming a metal thin film according to claim 2, wherein the central metal is tungsten and has a vapor pressure at 100° C. of 3.6 Torr or more.

21. The complex for forming a metal thin film according to claim 1 or 2, which is used in an atomic layer deposition method.

22. 3. An atomic layer deposition method, comprising using the complex according to claim 1 or 2 as a raw material compound.

23. 23. The atomic layer deposition method according to claim 22, wherein a film formation temperature during film formation using the complex according to claim 1 or 2 is 200° C. or less.

24. 23. The atomic layer deposition method of claim 22 for use in the manufacture of a semiconductor substrate.

25. 1. A method for selecting a precursor complex for use in atomic layer deposition, comprising the steps of: The atomic polarizability of the central metal is 45 to 51. The polarization volume is 200 or less, The relative dielectric constant is 2.20 or less, Surface charge density is 0.007 e / Å ２ The area of ​​the molecule is 10% or less of the total area of ​​the molecule, or the surface charge density is -0.007 e / Å ２ The area of ​​the following molecule is less than 10% of the total area of ​​the molecule: and selecting a complex wherein

26. 1. A method for selecting a precursor complex for use in atomic layer deposition, comprising the steps of: The atomic polarizability of the central metal is 52 to 90. The polarization volume is 220 or less, The relative dielectric constant is 2.50 or less, Surface charge density is 0.007 e / Å ２ The area of ​​the molecule is 10% or less of the total area of ​​the molecule, or the surface charge density is -0.007 e / Å ２ The area of ​​the following molecule is less than 10% of the total area of ​​the molecule: and selecting a complex wherein

27. 26. The method of claim 25, wherein the vapor pressure is 1.0 Torr or greater at 100°C.

28. 26. The method of claim 25, wherein the central metal of the complex is cobalt, nickel, or copper.

29. 27. The method of claim 26, wherein the vapor pressure is 0.6 Torr or greater at 100°C.

30. 27. The method of claim 26, wherein the central metal of the complex is molybdenum, ruthenium, or tungsten.

31. 27. The method of claim 25 or 26, wherein the polarization volume, dielectric constant, surface charge density and vapor pressure of the complex are determined by simulation.

32. The method according to claim 31 , wherein the simulation is at least one of a COSMO-SAC method, a DFT method, and an AMS method.

33. The method according to claim 32, wherein the COSMO-SAC method in the simulation is a modified COSMO-SAC method.

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