Method for producing metal or metalloid-containing films

Abstract

The present invention is in the field of methods for preparing inorganic metal- or semi-metal-containing films. The methods include: (a) depositing a gaseous metal or metalloid-containing compound onto a solid substrate; (b) treating a solid substrate with a compound of general formula (I), (II), (III), (IV), (V), (VI) or (VII) in a gaseous state; [Formula 1] TIFF2022536116000043.tif5398 TIFF2022536116000044.tif4690 (wherein A is NR or O, E is CR″, CNR″2, N, PR″2 or SOR″; G is CR' or N; R is an alkyl group, an alkenyl group, an aryl group, or a silyl group; R' and R'' are hydrogen, alkyl, alkenyl, aryl, or silyl groups. and contacting the compound of Includes:

Description

[Technical Field]

[0001] The present invention is in the field of methods, particularly atomic layer deposition, for producing inorganic metal- or semi-metal-containing films on substrates. [Background technology]

[0002] For example, in the semiconductor industry, miniaturization is driving the need for inorganic thin films on substrates, while the quality requirements for such films are becoming increasingly stringent. Thin films of metals or metalloids are used for various purposes, such as barrier layers, conductive functions, or capping layers. Several methods for forming metal or metalloid films are known. One method involves depositing a film-forming compound onto a substrate from a gaseous state. To convert metal or metalloid atoms into a gaseous state at moderate temperatures, it is necessary to provide volatile precursors, for example, by complexing the metal or metalloid with a suitable ligand. These precursors must be sufficiently stable against evaporation, yet reactive enough to react with the surface to be deposited.

[0003] EP 3 121 309 A1 discloses a method for depositing aluminum nitride films from a tris(dialkylamino)aluminum precursor, however this precursor is not stable enough for applications requiring high quality films.

[0004] To convert the deposited metal or metalloid complex to a metal or metalloid film, it is usually necessary to expose the deposited metal or metalloid complex to a reducing agent. Typically, hydrogen gas is used to convert the deposited metal or metalloid complex to a metal or metalloid film. While hydrogen works well as a reducing agent for relatively noble metals such as copper or silver, it does not produce satisfactory results with more electropositive metals such as titanium or aluminum.

[0005] WO 2013 / 070 702 A1 discloses a method for depositing metal films using aluminum hydride coordinated with diamines as reducing agents, which generally give good results, but for demanding applications, higher vapor pressure, stability and / or reduction potential are required.

[0006] N. Kuhn et al., Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 626 (2000), pp. 1387-1392, disclose vinamidine-alane complexes, but their suitability for preparing inorganic metal- or metalloid-containing films is not recognized by the authors. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] EP 3 121 309 A1 [Patent Document 2] WO 2013 / 070 702 A1 [Non-patent literature]

[0008] [Non-Patent Document 1] N. Kuhn et al., Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 626 (2000), pp. 1387-1392 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, it was an object of the present invention to provide a method for preparing inorganic metal- or metalloid-containing films with low impurities in the film. The starting material is easy to handle; in particular, it is possible to evaporate it with minimal decomposition. Furthermore, the starting material does not decompose at the deposition surface under process conditions, but at the same time is sufficiently reactive to participate in surface reactions. To avoid contamination of the film, all reaction by-products are volatile. Furthermore, the method can be tailored so that the metal or metalloid atoms in the starting material are volatile or incorporated into the film. Furthermore, the method is versatile and can be applied to the production of a wide variety of metals, including electropositive metal or metalloid films. [Means for solving the problem]

[0010] These objectives are: (a) depositing a gaseous metal or metalloid-containing compound onto a solid substrate; (b) treating a solid substrate with a compound of general formula (I), (II), (III), (IV), (V), (VI) or (VII) in a gaseous state;

[0011] [ka] TIFF0007768506000002.tif4690 (wherein A is NR or O, E is CR″, CNR″2, N, PR″2 or SOR″; G is CR' or N; R is an alkyl group, an alkenyl group, an aryl group, or a silyl group; R' and R'' are hydrogen, alkyl, alkenyl, aryl, or silyl groups. and contacting the compound of This was achieved by a method for preparing an inorganic metal- or semi-metal-containing film, comprising:

[0012] The present invention further relates to the use of a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) as a reducing agent in a vapor deposition process. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows the results of the thermogravimetric analysis. DETAILED DESCRIPTION OF THE INVENTION

[0014] Preferred embodiments of the invention can be found in the specification and claims. Combinations of the different embodiments are within the scope of the invention.

[0015] The method according to the present invention is suitable for preparing inorganic metal- or metalloid-containing films. Inorganic in the context of the present invention refers to a material containing at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight, and especially at least 30% by weight of at least one metal or metalloid. Typically, inorganic films contain carbon only in the form of a carbide phase, including a mixed carbide phase, such as a nitride carbide phase. The carbon content of carbon not part of the carbide phase in the inorganic film is preferably less than 5% by weight, more preferably less than 1% by weight, and especially less than 0.2% by weight. Preferred examples of inorganic metal- or metalloid-containing films include metal or metalloid nitride films, metal or metalloid carbide films, metal or metalloid carbonitride films, metal or metalloid alloy films, intermetallic compound films, or films containing mixtures thereof.

[0016] The film prepared by the method of the present invention contains a metal or metalloid. The film can contain one metal or metalloid, or two or more metals and / or metalloids. Metals include Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, and Bi. Metalloids include B, Si, Ge, As, Sb, Se, and Te. Preferably, the metal or metalloid is more electropositive than Cu, and more preferably more electropositive than Ni. In particular, the metal or semimetal is Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al or Si.

[0017] The solid substrate can be any solid material. These include, for example, metals, semi-metals, oxides, nitrides, and polymers. The substrate can also be a mixture of different materials. Examples of metals include aluminum, steel, zinc, and copper. Examples of semi-metals include silicon, germanium, and gallium arsenide. Examples of oxides include silicon dioxide, titanium dioxide, and zinc oxide. Examples of nitrides include silicon nitride, aluminum nitride, titanium nitride, and gallium nitride. Examples of polymers include polyethylene terephthalate (PET), polyethylene naphthalene-dicarboxylic acid (PEN), and polyamide.

[0018] The solid substrate can have any shape. These include sheets, plates, films, fibers, and substrates with particles of various sizes, grooves, or other depressions. The solid substrate can have any size. If the solid substrate has a particulate shape, the size of the particles can range from less than 100 nm to several centimeters, preferably 1 μm to 1 mm. It is preferable to keep the particles or fibers moving while the metal- or metalloid-containing compound is being deposited on them to prevent them from sticking together. This can be achieved, for example, by stirring, rotating drum, or fluidized bed techniques.

[0019] According to the present invention, a solid substrate is contacted with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) in the gas phase. R' in the compound of general formula (I) or (II) is hydrogen, an alkyl group, an alkenyl group, an aryl group, or a silyl group, preferably hydrogen or an alkyl group, particularly hydrogen, methyl, or ethyl. R' may be the same or different from one another. Preferably, all R' are the same.

[0020] The alkyl group may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylpentyl, neopentyl, 2-ethylhexyl, cyclopropyl, cyclohexyl, indanyl, and norbornyl. Preferably, the alkyl group is a C1-C8 alkyl group, more preferably a C1-C6 alkyl group, and particularly a C1-C4 alkyl group, such as methyl, ethyl, isopropyl, or tert-butyl.

[0021] Alkenyl groups contain at least one carbon-carbon double bond. This double bond can include the carbon atom where R' is attached to the rest of the molecule, or it can be located further away from where R' is attached to the rest of the molecule. Alkenyl groups can be straight-chain or branched. Examples of straight-chain alkenyl groups containing a double bond including the carbon atom where R' is attached to the rest of the molecule include 1-ethenyl, 1-propenyl, 1-n-butenyl, 1-n-pentenyl, 1-n-hexenyl, 1-n-heptenyl, and 1-n-octenyl. Examples of straight-chain alkenyl groups containing a double bond located further away from where R' is attached to the rest of the molecule include 1-n-propen-3-yl, 2-buten-1-yl, 1-buten-3-yl, 1-buten-4-yl, and 1-hexen-6-yl. Examples of branched alkenyl groups containing a double bond involving the carbon atom where R' is attached to the remainder of the molecule include 1-propen-2-yl, 1-n-buten-2-yl, 2-buten-2-yl, cyclopenten-1-yl, and cyclohexen-1-yl. Examples of branched alkenyl groups containing a double bond that is positioned further away from where R' is attached to the remainder of the molecule include 2-methyl-1-buten-4-yl, cyclopenten-3-yl, and cyclohexen-3-yl. Examples of alkenyl groups with more than one double bond include 1,3-butadien-1-yl, 1,3-butadien-2-yl, and cyclopentadien-5-yl.

[0022] Aryl groups include aromatic hydrocarbons such as phenyl, naphthalyl, anthracenyl, and phenanthrenyl, and heteroaromatic groups such as pyrryl, furanyl, thienyl, pyridinyl, quinoyl, benzofuryl, benzothiophenyl, and thienothienyl. A combination of these groups or groups, such as biphenyl, thienophenyl, or furanylthienyl, can also be used. The aryl group can be substituted with, for example, a halogen such as fluoride, chloride, bromide, or iodide; a pseudohalogen such as cyanide, cyanate, or thiocyanate; an alcohol; or an alkyl or alkoxy chain. Aromatic hydrocarbons are preferred, and phenyl is more preferred.

[0023] A silyl group is typically a silicon atom having three substituents. Preferably, the silyl group has the formula SiX3 (wherein X is, independently of one another, hydrogen, an alkyl group, an aryl group, or a silyl group). All three Xs can be the same, or two Xs can be the same and the remaining Xs can be different, or all three Xs can be different from one another, preferably all Xs can be the same. The alkyl group and aryl group are as described above. Examples of silyl groups include SiH3, methylsilyl, trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-isopropylsilyl, tricyclohexylsilyl, dimethyl-tert-butylsilyl, dimethylcyclohexylsilyl, methyl-di-isopropylsilyl, triphenylsilyl, phenylsilyl, dimethylphenylsilyl, and pentamethyldisilyl.

[0024] A in the compounds of general formula (I), (II), (III) or (IV) is NR or O, i.e., a nitrogen atom or an oxygen atom bearing a substituent R. R is an alkyl group, an alkenyl group, an aryl group or a silyl group. The same definition as for R' above applies. Preferably, R is an alkyl group or a silyl group, more preferably methyl, ethyl, isopropyl, sec-butyl, tert-butyl or trimethylsilyl, in particular tert-butyl or trimethylsilyl.

[0025] E in the compounds of general formula (III) or (IV) is CR", CNR", N, PR" or SOR", i.e., a carbon atom bearing one substituent R", or a carbon atom bonded to a nitrogen atom bearing two substituents R", a nitrogen atom, a phosphorus atom bearing two substituents R", or a sulfur atom bearing an oxygen atom and a substituent R" via a double bond. The same definition as for R' above applies. Preferably, R" is an alkyl or aryl group, in particular methyl or ethyl.

[0026] All of R, R', and R'' can be separate substituents. Alternatively, two of R, R', and R'' can together form a ring, preferably a 4- to 8-membered ring, especially a 5- or 6-membered ring.

[0027] Preferably, in the compounds of general formula (I), the central R', ie the R' at the 3-position of the ligand, is H. Compounds of general formula (I) include the following general formula:

[0028] [ka]

[0029] Preferred examples of compounds of formula (I) with reference to these formulae are shown in the table below.

[0030] [Table 1]

[0031] iPr represents iso-propyl, sBu represents sec-butyl, tBu represents tert-butyl, TMS represents trimethylsilyl, and DIP represents 2,6-diisopropylphenyl.

[0032] The synthesis of some of the compounds of general formula (I) is described, for example, by Z. Yang in Journal of the American Chemical Society, Vol. 138 (2016), pp. 2548-2551, or by S. Harder in Chemical Communications, Vol. 47 (2011), pp. 11945-11947, or by N. Kuhn in Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 626 (2000), pp. 1387-1392.

[0033] Preferably, the central R' in the compound of general formula (II) is H. The compound of general formula (II) comprises the following general formula:

[0034] [ka]

[0035] Preferred examples of compounds of formula (II) with reference to these formulae are shown in the table below.

[0036] [Table 2]

[0037] iPr represents iso-propyl, sBu represents sec-butyl, tBu represents tert-butyl, TMS represents trimethylsilyl, and DIP represents 2,6-diisopropylphenyl.

[0038] The synthesis of some of the compounds of general formula (II) is described, for example, by P. Kuo in European Journal of Inorganic Chemistry, Vol. 24 (2004), pp. 4898-4906.

[0039] An example of a compound in which two R's together form a ring is compound IIc-8 disclosed in KR 2016 / 116 180 A.

[0040] [ka]

[0041] Compounds of general formula (III) include the following general formula:

[0042] [ka] TIFF0007768506000009.tif39159 TIFF0007768506000010.tif39152

[0043] Preferably, the compound of general formula (III) is a compound of general formula (IIIc), (IIIe), (IIIf), (IIIj), (IIIm), (IIIp), or (IIIq). Preferred examples of the compound of general formula (III) with reference to these general formulas are shown in the table below.

[0044] [Table 3]

[0045] Et stands for ethyl, iPr stands for iso-propyl, sBu stands for sec-butyl, tBu stands for tert-butyl, TMS stands for trimethylsilyl, Ph stands for phenyl, and DIP stands for 2,6-diisopropylphenyl.

[0046] Compounds of general formula (IV) include the following homoleptic general formula:

[0047] [ka] TIFF0007768506000013.tif50159 TIFF0007768506000014.tif48148

[0048] Preferably, the compound of general formula (IV) is a compound of general formula (IVcc), (IVee), (IVff), (IVjj), (IVmm), (IVpp), (IVqq). With reference to these general formulas, preferred examples of the compound of general formula (IV) are shown in the following table.

[0049] [Table 4]

[0050] Et stands for ethyl, iPr stands for iso-propyl, sBu stands for sec-butyl, tBu stands for tert-butyl, TMS stands for trimethylsilyl, Ph stands for phenyl, and DIP stands for 2,6-diisopropylphenyl.

[0051] Some preferred heteroleptic compounds of general formula (IV) are shown below.

[0052] [ka] TIFF0007768506000017.tif40161 TIFF0007768506000018.tif42161 TIFF0007768506000019.tif46161 TIFF0007768506000020.tif44161 TIFF0007768506000021.tif46166 TIFF0007768506000022.tif48162 TIFF0007768506000023.tif47165 TIFF0007768506000024.tif45166 TIFF0007768506000025.tif45162 TIFF0007768506000026.tif47153 TIFF0007768506000027.tif45148 TIFF0007768506000028.tif44148 TIFF0007768506000029.tif44150 TIFF0007768506000030.tif43152 TIFF0007768506000031.tif4386

[0053] Particularly preferred heteroleptic compounds of general formula (IV) are compounds of general formula (IVce), (IVcf), (IVcj), (IVcm), (IVcp), (IVcq), (IVef), (IVej), (IVem), (IVep), (IVeq), (IVfj), (IVfm), (IVfp), (IVfq), (IVjm), (IVjp), (IVjq), (IVpq).

[0054] The synthesis of some of the compounds of general formula (IV) is described, for example, by A. Brazeau in Inorganic Chemistry, Vol. 45 (2006), pp. 2276-2281, or by B. Nekoueishahraki in Inorganic Chemistry, Vol. 48 (2009), pp. 9174-9179, or by R. Duchateau in Chemical Communications, Vol. 2 (1996), pp. 223-224, or by M. Cole in Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 641 (2015), pp. 2233-2244.

[0055] Compounds of general formula (V) include the following general formula:

[0056] [ka]

[0057] With reference to these general formulas, preferred examples of compounds of general formula (V) are shown in the following table.

[0058] [Table 5]

[0059] Et stands for ethyl, iPr stands for iso-propyl, sBu stands for sec-butyl, tBu stands for tert-butyl, TMS stands for trimethylsilyl, Ph stands for phenyl, and DIP stands for 2,6-diisopropylphenyl.

[0060] Compounds of general formula (VI) include the following general formula:

[0061] [ka]

[0062] With reference to these general formulas, preferred examples of the compound of general formula (VI) are shown in the following table.

[0063] [Table 6] TIFF0007768506000036.tif122111

[0064] Et stands for ethyl, iPr stands for iso-propyl, sBu stands for sec-butyl, tBu stands for tert-butyl, TMS stands for trimethylsilyl, Ph stands for phenyl, and DIP stands for 2,6-diisopropylphenyl.

[0065] In compounds of general formula (VII), the central aluminum atom is bonded to two radical monoanionic ligands derived from 1,4-diazabutadiene or 1,2,4-triazabutadiene. Compounds of general formula (VII) include the following general formula:

[0066] [ka]

[0067] With reference to these general formulas, preferred examples of the compound of general formula (VII) are shown in the following table.

[0068] [Table 7] TIFF0007768506000039.tif122112

[0069] Et stands for ethyl, iPr stands for iso-propyl, sBu stands for sec-butyl, tBu stands for tert-butyl, TMS stands for trimethylsilyl, Ph stands for phenyl, and DIP stands for 2,6-diisopropylphenyl.

[0070] Preferably, R does not have a hydrogen atom at position 1, i.e., R does not have a hydrogen atom bonded to a nitrogen or oxygen atom and therefore to an atom beta to the aluminum atom. Also preferably, R" does not have a hydrogen atom at position 1. More preferably, both R and R" do not have a hydrogen atom at position 1. Examples include alkyl groups having two alkyl side groups at position 1, i.e., 1,1-dialkylalkyl, such as tert-butyl and 1,1-dimethylpropyl; alkyl groups having two halogens at position 1, such as trifluoromethyl, trichloromethyl, and 1,1-difluoroethyl; trialkylsilyl groups, such as trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl; and aryl groups, especially phenyl, or alkyl-substituted phenyl, such as 2,6-diisopropylphenyl and 2,4,6-triisopropylphenyl. Alkyl groups having no hydrogen atom at position 1 are particularly preferred.

[0071] The compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) preferably have a molecular weight of 1000 g / mol or less, more preferably 800 g / mol or less, even more preferably 600 g / mol or less, and especially 500 g / mol or less.

[0072] Preferably, the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) have a melting point in the range of −80 to 125° C., preferably −60 to 80° C., even more preferably −40 to 50° C., and especially −20 to 20° C. It is advantageous if the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) are melted to give a clear liquid that does not change up to their decomposition temperature.

[0073] The compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) preferably have a decomposition temperature of at least 80°C, more preferably at least 100°C, particularly at least 120°C, for example at least 150°C. In many cases, the decomposition temperature is 250°C or less. The compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) have a high vapor pressure. The vapor pressure is preferably at least 1 mbar at 200°C, more preferably at 150°C, particularly at 120°C. Usually, the temperature at which the vapor pressure is 1 mbar is at least 50°C.

[0074] To achieve the best results, the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) used in the method according to the present invention are used with high purity. High purity means that the materials used contain at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight, and especially at least 99% by weight, of compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) or metal- or metalloid-containing compounds. Purity can be determined by elemental analysis according to DIN 51721 (Pruefung fester Brennstoffe - Bestimmung des Gehaltes an Höhlenstoff und Wasserstoff - Verfahren nach Radmacher-Hoverath, August 2001).

[0075] The compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) are contacted with the solid substrate from the gaseous state. This can be achieved, for example, by heating them to a high temperature. In either case, a temperature below the decomposition temperature of the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) must be selected. The decomposition temperature is the temperature at which the original compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) begin to change their chemical structure and composition. The heating temperature is preferably in the range of 0°C to 300°C, more preferably 10°C to 250°C, even more preferably 20°C to 200°C, and especially 30°C to 150°C.

[0076] Another method for converting a compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) into a gaseous state is direct liquid injection (DLI), as described, for example, in US 2009 / 0 226 612 A1. In this method, a compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) is typically dissolved in a solvent and sprayed with a carrier gas or in a vacuum. When the vapor pressure and temperature of the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) are sufficiently high and the pressure is sufficiently low, the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) will be converted into a gaseous state. A variety of solvents can be used, provided that the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) exhibits sufficient solubility in the solvent, such as at least 1 g / L, preferably at least 10 g / L, and more preferably at least 100 g / L. Examples of these solvents include coordinating solvents such as tetrahydrofuran, dioxane, diethoxyethane, and pyridine, or non-coordinating solvents such as hexane, heptane, benzene, toluene, or xylene. Mixtures of solvents are also suitable.

[0077] Alternatively, compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) can be converted to a gaseous state by direct liquid evaporation (DLE), as described, for example, by J. Yang et al. (Journal of Materials Chemistry, 2015). In this method, compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) are mixed with a solvent, such as a hydrocarbon such as tetradecane, and heated below the boiling point of the solvent. The solvent is evaporated, converting the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) to a gaseous state. This method has the advantage of not forming particulate contaminants on the surface.

[0078] It is preferred to convert the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) into a gaseous state under reduced pressure. In this way, the method of the present invention can usually be carried out at a low heating temperature, which results in reduced decomposition of the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII). It is also possible to use high pressure to extrude the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII) in a gaseous state toward a solid substrate. For this purpose, an inert gas such as nitrogen or argon is often used as a carrier gas. The pressure is preferably 10 bar to 10 bar. -7 millibar, more preferably 1 bar to 10 -3 It is in millibars, in particular between 1 and 0.01 mbars, for example 0.1 mbars.

[0079] Typically, a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) acts as a reducing agent in the method of the present invention. According to the present invention, a metal- or metalloid-containing compound is deposited on a solid substrate from a gaseous state before contacting with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII). The metal- or metalloid-containing compound is usually reduced to a metal, metal nitride, metal carbide, metal carbonitride, metal alloy, intermetallic compound, or mixtures thereof. Metal films in the context of the present invention generally have a molecular weight of at least 10 ... 4 S / m, preferably at least 10 5 S / m, especially at least 10 6 It is a metal or semi-metal containing film with high electrical conductivity of S / m.

[0080] The compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) have a low tendency to form permanent bonds with the surface of the solid substrate on which the metal- or metalloid-containing compound is deposited. As a result, the metal- or metalloid-containing film is less likely to be contaminated with reaction by-products of the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII). Preferably, the metal- or metalloid-containing film contains less than 5 wt. % nitrogen, more preferably less than 1 wt. %, particularly less than 0.5 wt. %, e.g., less than 0.2 wt. % nitrogen in total.

[0081] The metal- or metalloid-containing compound contains at least one metal or metalloid atom. Metals include Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, and Bi. Metalloids include B, Si, Ge, As, Sb, Se, and Te. Preferably, the metal- or metalloid-containing compound contains a metal or metalloid that is more electropositive than Cu, and more preferably more electropositive than Ni. In particular, the metal- or metalloid-containing compound contains Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al, or Si. Two or more metal- or metalloid-containing compounds can be deposited simultaneously or sequentially on a surface. When two or more metal- or metalloid-containing compounds are deposited on a solid substrate, all of the metal- or metalloid-containing compounds can contain the same metal or metalloid, or different metals or metalloids, and preferably, they contain different metals or metalloids.

[0082] Suitable compounds containing metals or metalloids can be converted into gaseous state.These compounds include metal or metalloid alkyls, such as dimethylzinc, trimethylaluminum; metal alkoxylates, such as tetramethoxysilicon, tetraisopropoxyzirconium, or tetraisopropoxytitanium; metal or metalloid cyclopentadienyl complexes, such as pentamethylcyclopentadienyl-trimethoxytitanium or di(ethylcyclopentadienyl)manganese; metal or metalloid carbenes, such as tris(neopentyl)neopentylidenetantalum or bisimidazolidinylideneruthenium chloride; metal or metalloid halides, such as aluminum trichloride. tantalum pentachloride, titanium tetrachloride, molybdenum pentachloride, germanium tetrachloride, gallium trichloride, arsenic trichloride, or tungsten hexachloride; carbon monoxide complexes such as chromium hexacarbonyl or nickel tetracarbonyl; amine complexes such as bis(tert-butylimino)bis(dimethylamino)molybdenum, bis(tert-butylimino)bis(dimethylamino)tungsten, or tetrakis(dimethylamino)titanium; and diketonate complexes such as tris(acetylacetonato)aluminum or bis(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese. Metal or metalloid halides, particularly aluminum chloride, aluminum bromide, and aluminum iodide, are preferred. The molecular weight of the metal or metalloid-containing compound is preferably 1000 g / mol or less, more preferably 800 g / mol or less, and especially 600 g / mol or less, for example 500 g / mol or less.

[0083] Preferably, the method of the present invention is carried out as an atomic layer deposition (ALD) method. Preferably, the series of steps including (a) and (b) is carried out at least twice, more preferably at least five times, even more preferably at least 10 times, and particularly at least 50 times. In many cases, the series of steps including (a) and (b) is carried out 1000 times or less.

[0084] In general, it is preferable to purge the substrate and the surrounding equipment with an inert gas each time the solid substrate is contacted with a gaseous metal- or metalloid-containing compound or a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII). Preferred examples of inert gases include nitrogen and argon. Purging can be carried out for 1 second to 1 minute, preferably 5 to 30 seconds, more preferably 10 to 25 seconds, and particularly 15 to 20 seconds.

[0085] Preferably, the temperature of the substrate is 5°C to 40°C, for example 20°C, higher than the temperature at which the metal- or metalloid-containing compound is converted into a gaseous state. The temperature of the substrate is preferably from room temperature to 400°C, more preferably 100 to 300°C, for example 150 to 220°C.

[0086] Preferably, after depositing a metal or metalloid-containing compound on a solid substrate, and before contacting the solid substrate with the deposited metal or metalloid-containing compound with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII), the solid substrate with the deposited metal or metalloid-containing compound is contacted with an acid in the gas phase. Without being bound by theory, it is believed that protonation of the ligand of the metal or metalloid-containing compound promotes its decomposition and reduction. Suitable acids include hydrochloric acid and carboxylic acids, preferably carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, or trifluoroacetic acid, especially formic acid.

[0087] Alternatively, aluminum can be deposited from a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII). In this case, for example, the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) is adsorbed onto the surface of the solid substrate due to the presence of reactive groups such as OH groups on the surface of the solid substrate or the temperature of the solid substrate being sufficiently high. Preferably, the adsorbed compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) is decomposed.

[0088] The decomposition can be carried out in various ways. The temperature of the solid substrate can be raised above the decomposition temperature. In this case, the method of the present invention is a chemical vapor deposition (CVD) method. Typically, the solid substrate is heated to a temperature in the range of 300 to 1000°C, preferably 350 to 600°C.

[0089] Furthermore, the deposited compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) can be exposed to a plasma, such as oxygen plasma, hydrogen plasma, ammonia plasma, or nitrogen plasma; an oxidizing agent, such as oxygen, oxygen radicals, ozone, nitrous oxide (NO), nitric oxide (NO), nitrogen dioxide (NO), or hydrogen peroxide; ammonia or an ammonia derivative, such as tert-butylamine, isopropylamine, dimethylamine, methylethylamine, or diethylamine; hydrazine or a hydrazine derivative, such as N,N-dimethylhydrazine; a solvent, such as water, an alkane, or tetrachlorocarbon; or a boron compound, such as borane. The choice depends on the chemical structure of the desired layer. In the case of aluminum oxide, it is preferred to use an oxidizing agent, plasma, or water, particularly oxygen, water, oxygen plasma, or ozone. In the case of aluminum nitride, ammonia, hydrazine, a hydrazine derivative, nitrogen plasma, or ammonia plasma is preferred. In the case of aluminum boride, boron compounds are preferred, in the case of aluminum carbide, alkanes or tetrachlorocarbons are preferred, and in the case of aluminum carbonitride, mixtures containing alkanes, tetrachlorocarbons, ammonia and / or hydrazine are preferred.

[0090] Preferably, the method of the present invention comprises the following series of steps: (c) contacting a solid substrate with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII); (d) decomposing the adsorbed compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII); Preferably, the series of steps including (c) and (d) is performed at least twice, more preferably at least five times, even more preferably at least 10 times, and particularly at least 50 times. In many cases, the series of steps including (c) and (d) is performed 1000 times or less.

[0091] In this case, the temperature of the substrate is preferably 5° C. to 40° C., for example 20° C. higher than the temperature at which the metal- or metalloid-containing compound is converted into a gaseous state. The temperature of the substrate is preferably room temperature to 400° C., more preferably 100 to 300° C., for example 150 to 220° C.

[0092] When the substrate temperature in the method according to the present invention is maintained below the decomposition temperature of the metal- or metalloid-containing compound, a monolayer is typically deposited on the solid substrate. Once molecules of the metal- or metalloid-containing compound are deposited on the solid substrate, further deposition thereon is typically unlikely. Therefore, the deposition of the metal- or metalloid-containing compound on the solid substrate preferably represents a self-limiting process step. Typical layer thicknesses for self-limiting deposition process steps are 0.01 to 1 nm, preferably 0.02 to 0.5 nm, more preferably 0.03 to 0.4 nm, and especially 0.05 to 0.2 nm. The layer thickness is typically measured by ellipsometry, as described in PAS 1022 DE (References to the Optic and Material Engineering Standards Actuated by the European Commission; February 2004).

[0093] The exposure of the substrate to the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII), or the metal- or metalloid-containing compound, can be carried out for a period of time ranging from milliseconds to minutes, preferably 0.1 seconds to 1 minute, and particularly 1 second to 10 seconds. The longer the exposure time of the solid substrate to the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII), or the metal- or metalloid-containing compound, at a temperature below the decomposition temperature of the compound of formula (I), (II), (III), (IV), (V), (VI), or (VII), or the metal- or metalloid-containing compound, the more ordered the film formed, with fewer defects.

[0094] A particular advantage of the process according to the invention is that the compounds of general formula (I), (II), (III), (IV), (V), (VI), or (VII) are very versatile, which allows for a wide range of variation in the process parameters, and therefore the process according to the invention includes both CVD and ALD processes.

[0095] The method according to the present invention results in inorganic metal- or semimetal-containing films. The films can be monolayers of metal or can be as thick as 0.1 nm to 1 μm, preferably 0.5 to 50 nm. The films may contain defects such as holes. However, these defects typically occupy less than half of the surface area covered by the film. Preferably, the films have a very uniform thickness, meaning that there is little variation in thickness at different locations on the substrate, typically less than 10%, preferably less than 5%. Furthermore, the films are preferably conformal films on the surface of the substrate. Suitable methods for determining thickness and uniformity are XPS or ellipsometry.

[0096] The films obtained by the method according to the present invention can be used in electronic devices. The electronic devices can have structural features of various sizes, for example, from 1 nm to 100 μm, such as 10 nm, 14 nm, or 22 nm. The method for forming films for electronic devices is particularly suitable for very fine structures. Therefore, electronic devices with sizes less than 1 μm are preferred. Examples of electronic devices include field-effect transistors (FETs), solar cells, light-emitting diodes, sensors, or capacitors. In optical devices such as light-emitting diodes or optical sensors, the films obtained by the method according to the present invention are useful for increasing the refractive index of light-reflecting layers.

[0097] A preferred electronic device is a transistor. Preferably, the film functions as a chemical barrier metal in the transistor. A chemical barrier metal is a material that reduces diffusion of adjacent layers while maintaining electrical connectivity. [Example]

[0098] Example 1a: 4-(isopropylamino)pent-3-en-2-one ( i Synthesis of PrNacacH A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in 100 mL of ethanol was added dropwise to a solution of isopropylamine (8.7 mL, 0.1 mol) in 100 mL of ethanol. The resulting pale yellow solution was refluxed in a 250 mL round-bottom flask at 100 °C for 18 hours. The dark yellow solution was reduced in volume under reduced pressure. The residue was fractionally distilled at 78 °C under reduced pressure (0.8 Torr). i PrNacacH (11.859 g, 84% yield) was obtained as a pale yellow liquid.

[0099] 1 H NMR (400 MHz, C6D6) δ = 0.82 (d, 6H), 1.51 (s, 3H), 1.96 (s, 3H), 3.19 (m, 1H), 4.83 (s, 1H), 11.10 (s, 1H). 13 C{ 1H}NMR(100MHz,C6D6)δ=18.59,24.07,29.23,44.69,95.47,161.17,194.26.

[0100] Example 1b: N,N'-diisopropyl-2,4-pentanediketimine ( i Synthesis of PrNacNacH in dimethyl sulfate (6 mL, 0.063 mol) i A solution of PrNacacH (5.376 g, 0.038 mol) was stirred at room temperature for 5 minutes and then allowed to stand for 24 hours, yielding a viscous orange solution. Subsequently, excess isopropylamine (7 mL, 0.081 mol) was added and stirred at room temperature for 1 hour, resulting in the solution darkening in color. A mixture of excess sodium methoxide in methanol (11 mL, 0.048 mol) was added and stirred at room temperature for 1 hour. The volatile components were evaporated under reduced pressure, and then water (40 mL) was added to the resulting product. The contents of the flask were transferred to a separatory funnel. The crude product was extracted with pentane (10 × 40 mL), and the combined organic fractions were dried over anhydrous Na2SO4. The solution was filtered through a fluted filter paper to yield a clear solution. The volatile components were removed under reduced pressure. i PrNacNacH (2.195 g) was obtained as an orange oil.

[0101] 1 H NMR (400 MHz, C6D6) δ = 1.13 (d, 12H), 1.73 (s, 6H), 3.48 (m, 2H), 4.48 (s, 1H), 11.66 (s, 1H).

[0102] 13 C{ 1 H}NMR(100MHz,C6D6)δ=19.16,25.44,47.35,94.98,158.33.

[0103] This crude product was used in the synthesis of aluminum complexes without further purification.

[0104] Example 1c: Synthesis of Compound Ia-1 A solution of AlCl3 (0.372 g, 2.8 mmol) in 30 mL of diethyl ether was cannulated into a stirred solution of LiAlH4 (0.334 g, 8.4 mmol) in 30 mL of diethyl ether in an ice bath at 0 °C. The resulting cloudy solution was warmed to room temperature, stirred for 40 min, and then recooled to -30 °C. Next, 40 mL of diethyl ether was added to the solution. i A solution of PrNacNacH (2.035 g, 11.16 mmol) was added dropwise. The resulting mixture was stirred at room temperature for 18 h and then filtered through a 2 cm plug of Celite on a coarse glass frit. The diethyl ether was evaporated from the filtrate under reduced pressure to collect a dark yellow, creamy product. The crude product was purified by sublimation under reduced pressure at 50 °C to give compound Ia-1 as pale yellow crystals (1.251 g, 53% yield). mp = 62-63 °C.

[0105] 1 H NMR (400 MHz, C6D6) δ = 1.31 (d, 12H), 1.56 (s, 6H), 3.48 (m, 2H), 4.41 (s, 1H).

[0106] 13 C{ 1 H}NMR(100MHz,C6D6)δ=21.88,23.12,50.59,97.73,166.96.

[0107] The results of the thermogravimetric analysis are shown in FIG.

[0108] Example 2a: 4-(sec-butylamino)pent-3-en-2-one ( s Synthesis of BuNacacH A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in 100 mL of ethanol was added dropwise to a solution of sec-butylamine (10 mL, 0.1 mol) in 100 mL of ethanol. The resulting pale yellow solution was refluxed in a 250 mL round-bottom flask at 100°C for 18 hours. The dark yellow solution was reduced in volume under reduced pressure. The residue was fractionally distilled at 0.8 Torr and 97°C. sBuNacacH was obtained as a pale yellow liquid (14.332 g, 92.3% yield).

[0109] 1 H NMR(400MHz,C6D6)δ=0.68(t,3H),0.80(d,3H),1.16(m,2H),1.51(s,3H),1.98(s,3H),3.00(m,1H),4.84(s,1H),11.13(s,1H).

[0110] 13 C{ 1 H}NMR(100MHz,C6D6)δ=10.69,18.86,21.95,29.23,31.12,50.35,95.51,161.63,194.30.

[0111] Example 2b: N,N'-di(sec-butyl)-2,4-pentanediketimine ( s Synthesis of BuNacNacH in dimethyl sulfate (4 mL, 0.043 mol) s A solution of BuNacacH (4.005 g, 0.026 mol) was stirred at room temperature for 5 minutes and then allowed to stand for 24 hours, resulting in a viscous orange solution. Excess sec-butylamine (6 mL, 0.059 mol) was then added, and the solution was stirred at room temperature for an additional 2 hours. A mixture of excess sodium methoxide in methanol (7.5 mL, 0.033 mol) was added, and the mixture was stirred for 1 hour. The volatile components were evaporated under reduced pressure, and water (20 mL) was added to the resulting product. The contents of the flask were transferred to a separatory funnel. The crude product was extracted with pentane (10 × 35 mL), and the combined organic fractions were dried over anhydrous Na2SO4. The solution was filtered through fluted filter paper. Residual solvent was evaporated under reduced pressure to give a crude product. s BuNacNacH (5.810 g) was obtained. The crude product was distilled at 85-87°C and 0.8 Torr. s BuNacNacH was obtained as a pale yellow liquid (2.405 g, 45% yield).

[0112] 1H NMR(400MHz,C6D6)δ=0.90(t,6H),1.07(d,6H),1.46(m,4H),1.73(s,6H),3.27(m,2H),4.45(s,1H),11.52(s,1H).

[0113] 13 C{ 1 H}NMR(100MHz,C6D6)δ=11.15,19.43,23.04,32.54,52.98,95.16,158.67.

[0114] Example 2c: Synthesis of Compound Ia-2 A solution of AlCl3 (0.381 g, 2.85 mmol) in 30 mL of diethyl ether was cannulated into a stirred solution of LiAlH4 (0.343 g, 8.57 mmol) in 30 mL of diethyl ether in an ice bath at 0 °C. The resulting cloudy solution was warmed to room temperature, stirred for 40 min, and then recooled to -30 °C. Next, 40 mL of diethyl ether was added to the solution. s A solution of BuNacNacH (2.405 g, 11.43 mmol) was added dropwise. The resulting mixture was stirred at room temperature for 18 hours and then filtered through a 2 cm plug of Celite on a coarse glass frit. Diethyl ether was evaporated from the filtrate under reduced pressure to collect a yellow creamy product. The crude product was purified by sublimation at 45 °C and 0.8 Torr to give compound Ia-2 as pale yellow crystals (0.967 g, 35.5% yield). mp = 40 °C.

[0115] 1 H NMR(400MHz,C6D6)δ=0.83(6H,2CH(CH3)CH2CH3),1.32(6H,2CH(CH3)CH2CH3),1.59(8H,2β-C(CH 3)+2CH(CH3)CHH'CH3),2.00(2H,2CH(CH3)CHH'CH3),3.23(2H,CH(CH3)CH2CH3),4.50(1H,α-CH).

[0116] 13 C{ 1H}NMR(100MHz,C6D6)δ=12.10,21.54,22.46,30.43,56.80,97.91,167.23.

[0117] The results of the thermogravimetric analysis are shown in FIG.

Claims

1. (a) depositing a gaseous metal or metalloid-containing compound onto a solid substrate; (b) treating the solid substrate with a compound represented by general formula (I), (II), (III), (IV), (V), (VI) or (VII) in a gaseous state; 【Chemistry 1】 wherein A is NR or O; E is CR'', CNR'' ２ ,N,PR'' ２ or SOR″, G is CR′ or N; R is an alkyl group, an alkenyl group, an aryl group, or a silyl group; wherein R′ and R″ are hydrogen, alkyl groups, alkenyl groups, aryl groups, or silyl groups; 1. A method for preparing an inorganic metal- or metalloid-containing film, comprising: the metal- or metalloid-containing compound in a gaseous state contains Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al, or Si; A method wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a molecular weight of 500 g / mol or less.

2. 2. The method of claim 1, wherein R is methyl, ethyl, iso-propyl, sec-butyl, tert-butyl, trimethylsilyl.

3. 3. The method of claim 1 or 2, wherein R does not have a hydrogen atom at the 1-position.

4. 4. The method according to any one of claims 1 to 3, wherein R' at the 3-position of the ligand in the compound of general formula (I) or (II) is H.

5. 5. The method of any one of claims 1 to 4, wherein the metal or metalloid containing compound is a metal or metalloid halide.

6. 6. The method according to any one of claims 1 to 5, wherein the sequence of steps comprising (a) and (b) is carried out at least twice.

7. 7. The method of claim 1, wherein the method is an atomic layer deposition method.

8. 8. The method of any one of claims 1 to 7, wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a vapor pressure of at least 1 mbar at a temperature of 200°C.

9. 9. The method of any one of claims 1 to 8, wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a melting point of -80°C to 125°C.

10. 10. The method of any one of claims 1 to 9, wherein the inorganic metal- or semi-metal-containing film comprises a metal, a metal nitride, a metal carbide, a metal carbonitride, a metal alloy, an intermetallic compound, or a mixture thereof.

11. General formula (I), (II), (III), (IV), (V), (VI), or (VII) 【Chemistry 2】 wherein A is NR or O; E is CR'', CNR'' ２ ,N,PR'' ２ or SOR″, G is CR′ or N; R is an alkyl group, an alkenyl group, an aryl group, or a silyl group; wherein R' and R'' are hydrogen, alkyl, alkenyl, aryl, or silyl groups, as a reducing agent in a vapor deposition process to react with a gaseous metal- or metalloid-containing compound on a solid substrate after said solid substrate has been deposited, comprising: the metal- or metalloid-containing compound in a gaseous state contains Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al, or Si; A method wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a molecular weight of 500 g / mol or less.

12. The use according to claim 11, wherein the vapor deposition method is atomic layer deposition.

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