Method for manufacturing metal or metal-containing films

Abstract

The present invention belongs to the field of methods for manufacturing inorganic metal or metalloid-containing films. The method (a) a step of depositing a gaseous metal or metalloid-containing compound on a solid substrate, and (b) a step of contacting the solid substrate with a gaseous compound of the following chemical formulas I, II, III, IV, V, VI, or VII. Includes: A is NR or O, and E is CR", CNR"2, N, PR"2 or SOR" and, G is CR' or N, and R is an alkyl group, an alkeneyl group, an aryl group, or a silyl group, and R' and R" are hydrogen, alkyl groups, alkenyl groups, aryl groups, or silyl groups.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing an inorganic metal or semimetal-containing film on a substrate, particularly in the field of atomic layer deposition processes. Background Technology

[0002] For example, due to the ongoing miniaturization in the semiconductor industry, the need for thin inorganic films on substrates is increasing, while the requirements for the quality of these films are becoming more stringent. Thin metal or semimetal films are useful for various purposes, such as barrier layers, conductive properties, or capping layers. Several methods for manufacturing metal or semimetal films are known. One of them involves depositing a film-forming compound onto a substrate in a gaseous state. To make metal or semimetal atoms gaseous at a suitable temperature, it is necessary to provide a volatile precursor, for example, by complexing the metal or semimetal with a suitable ligand. Such a precursor must be sufficiently stable for evaporation, but on the other hand, it must be sufficiently reactive to react with the deposition surface.

[0003] EP 3 121 309 A1 discloses a process for depositing an aluminum nitride film from a tris(dialkylamino)aluminum precursor. However, the precursor is not sufficiently stable for applications requiring a high-quality film.

[0004] To convert a deposited metal or metalloid complex into a metal or metalloid film, it is generally 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 into a metal or metalloid film. Hydrogen works adequately well as a reducing agent for relatively precious metals, such as copper or silver, but does not yield satisfactory results for 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 a diamine as a reducing agent. While this reducing agent generally yields good results, for some demanding applications, higher vapor pressure, stability, and / or reduction potential are required.

[0006] Vinamidin-alane complexes are disclosed in the literature [N. Kuhn et al., Zeitschrift fur Anorganische und Allgemeine Chemie, volume 626 (2000) pages 1387-1392]. However, the authors did not recognize their suitability for preparing inorganic metal or metalloid-containing films.

[0007] Accordingly, the object of the present invention is to provide a method for manufacturing an inorganic metal or metalloid-containing film having low impurity content. The process material must be easy to handle; in particular, it must be possible to vaporize it with minimal possible decomposition. Furthermore, the process material must not decompose on the deposition surface under process conditions and must simultaneously possess sufficient reactivity to participate in surface reactions. All reaction byproducts must be volatile to avoid film contamination. Additionally, it must be possible to adjust the process so that the metal or metalloid atoms of the process material are volatile or incorporated into the film. Furthermore, the process must be versatile so that it can be applied to produce a wide range of various metals, including positively charged metal or metalloid films.

[0008] These purposes

[0009] (a) a step of depositing a gaseous metal or metalloid-containing compound on a solid substrate, and

[0010] (b) a step of contacting the solid substrate with a gaseous compound of the following chemical formulas I, II, III, IV, V, VI, or VII.

[0011] This was achieved by a method for manufacturing an inorganic metal or metalloid-containing film comprising:

[0012]

[0013] In the above formula,

[0014] A is NR or O, and

[0015] E is CR", CNR"2, N, PR"2 or SOR" and,

[0016] G is CR' or N, and

[0017] R is an alkyl group, an alkeneyl group, an aryl group, or a silyl group, and

[0018] R' and R" are hydrogen, alkyl groups, alkenyl groups, aryl groups, or silyl groups.

[0019] The present invention further relates to the use of a compound of formulas I, II, III, IV, V, VI, or VII as a reducing agent in a vapor deposition method. Specific details for implementing the invention

[0020] Preferred embodiments of the present invention can be found in the detailed description and claims. Combinations of different embodiments are within the scope of the present invention.

[0021] The method according to the present invention is suitable for manufacturing inorganic metal or semimetal-containing films. In the present invention, "inorganic" refers to a material containing at least 5 weight%, preferably at least 10 weight%, more preferably at least 20 weight%, and particularly at least 30 weight% of one or more metals or semimetals. The inorganic film typically contains only carbon in the form of a carbide phase, including a mixed carbide phase (e.g., a nitride carbide phase). The carbon content of carbon that is not part of the carbide phase in the inorganic film is preferably less than 5 weight%, more preferably less than 1 weight%, and particularly less than 0.2 weight%. Preferred examples of inorganic metal or semimetal-containing films are films containing a metal or semimetal nitride film, a metal or semimetal carbide film, a metal or semimetal carbonitride film, a metal or semimetal alloy film, an intermetallic compound film, or a mixture thereof.

[0022] A film produced by the method according to the present invention contains a metal or a metalloid. It is possible for the film to contain one metal or a metalloid, or more than one metal and / or metalloid. The 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. The metalloids include B, Si, Ge, As, Sb, Se, and Te. Preferably, the metal or metalloid is more positively charged than Cu, and more preferably more positively charged than Ni. In particular, metals or metalloids are Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al, or Si.

[0023] The solid substrate can be any solid material. This includes, for example, metals, metalloids, oxides, nitrides, and polymers. Additionally, the substrate may be a mixture of various materials. Examples of metals are aluminum, steel, zinc, and copper. Examples of metalloids are silicon, germanium, and gallium arsenide. Examples of oxides are silicon dioxide, titanium dioxide, and zinc oxide. Examples of nitrides are silicon nitride, aluminum nitride, titanium nitride, and gallium nitride. Examples of polymers are polyethylene terephthalate (PET), polyethylene naphthalene dicarboxylic acid (PEN), and polyamide.

[0024] The solid substrate may have any shape. This includes sheet plates, films, fibers, particles of various sizes, and substrates having trenches or other grooves. The solid substrate may be of any size. If the solid substrate has a particle form, the particle size may be in the range of less than 100 nm to several centimeters, preferably 1 μm to 1 mm. To prevent particles or fibers from sticking together while a metal or metalloid-containing compound is deposited on top, it is desirable to maintain their movement. This can be achieved, for example, by stirring, a rotary drum, or a fluidized bed technique.

[0025] According to the present invention, a solid substrate is brought into contact with a gaseous compound of formula I, II, III, IV, V, VI, or VII. R' of the compound of formula I or II is hydrogen, an alkyl group, an alkeneyl 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.

[0026] The alkyl group may be linear or branched. Examples of linear alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. Examples of branched alkyl groups are iso-propyl, iso-butyl, sec-butyl, tert-butyl, 2-methyl-pentyl, neo-pentyl, 2-ethyl-hexyl, cyclopropyl, cyclohexyl, indanyl, and nobonyl. Preferably, the alkyl group is a C1 to C8 alkyl group, more preferably a C1 to C6 alkyl group, particularly a C1 to C4 alkyl group, such as methyl, ethyl, iso-propyl, or tert-butyl.

[0027] An alkenyl group contains one or more carbon-carbon double bonds. The double bond may include an atom that allows R' to be bonded to the rest of the molecule, or it may be located further away from where R' is bonded to the rest of the molecule. The alkenyl group may be linear or branched. Examples of linear alkenyl groups in which the double bond includes a carbon atom that allows R' to be bonded 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 linear alkenyl groups in which the double bond is located further away from where R' is bonded 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-hexeny-6-yl. Examples of branched alkenyl groups containing a carbon atom such that the double bond R' is bonded to the rest of the molecule include 1-propene-2-yl, 1-n-butene-2-yl, 2-butene-2-yl, cyclopentene-1-yl, and cyclohexene-1-yl. Examples of branched alkenyl groups in which the double bond is located further away from the position where R' is bonded to the rest of the molecule include 2-methyl-1-butene-4-yl, cyclopentene-3-yl, and cyclohexene-3-yl. Examples of alkenyl groups having more than one double bond include 1,3-butadiene-1-yl, 1,3-butadiene-2-yl, and cyclopentadiene-5-yl.

[0028] The aryl group includes aromatic hydrocarbons, such as phenyl, naphthalyl, anthracenyl, and phenanthrenyl groups, and heteroaromatic groups, such as pyryl, furanyl, thienyl, pyridinyl, quinoyl, benzofuryl, benzothiophenyl, and thienothienyl. Some of these groups or combinations of these groups, such as biphenyl, thienophenyl, or furanylthienyl, are also possible. The aryl group may be substituted, for example, by halogens, such as fluoride, chloride, bromide, and iodide; by pseudohalogens, such as cyanide, cyanate, and thiocyanate; by alcohols; or by alkyl chains or alkoxy chains. Aromatic hydrocarbons are preferred, and phenyl is more preferred.

[0029] A silyl group is typically a silicon atom having three substituents. Preferably, the silyl group has the chemical formula SiX3, where X is independently hydrogen, an alkyl group, an aryl group, or a silyl group. It is possible for all three Xs to be the same, for two Xs to be the same and the remaining X to be different, or for all three Xs to be different from each other; preferably, all Xs are the same. The alkyl and aryl groups are as described above. Examples of silyl groups include SiH3, methylsilyl, trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-iso-propylsilyl, tricyclohexylsilyl, dimethyl-tert-butylsilyl, dimethylcyclohexylsilyl, methyl-di-iso-propylsilyl, triphenylsilyl, phenylsilyl, dimethylphenylsilyl, and pentamethyldisylyl.

[0030] A of the compound of formula I, II, III, or IV is NR or O, that is, a nitrogen atom or an oxygen atom having the substituent R. R is an alkyl group, an alkenyl group, an aryl group, or a silyl group. The same definition applies to R' described above. Preferably, R is an alkyl or silyl group, more preferably methyl, ethyl, iso-propyl, sec-butyl, tert-butyl, or trimethylsilyl, particularly tert-butyl or trimethylsilyl.

[0031] E of a compound of formula III or IV is CR", CNR"2, N, PR"2, or SOR", that is, a carbon atom having one substituent R", a carbon atom bonded to a nitrogen atom having two substituents R", a nitrogen atom, a phosphorus atom having two substituents R", or an oxygen atom through a double bond and a sulfur atom having a substituent R". The same definition applies to R' described above. Preferably, R" is an alkyl or aryl group, in particular methyl or ethyl.

[0032] It is possible for R, R', and R" to all be distinct substituents. Alternatively, it is possible for two of R, R', and R" to form a ring together, preferably a 4- to 8-membered ring, in particular a 5-membered or 6-membered ring.

[0033] Preferably, in the compound of formula I, the center R', i.e., the R' at the 3rd position of the ligand, is H. The compound of formula I includes the following formula:

[0034] .

[0035] Preferred examples of compounds of Formula I with respect to these formulas are provided in the table below:

[0036]

[0037] Synthesis of some of the compounds of Chemical Formula I is described, for example, in the literature [Z. Yang, the Journal of the American Chemical Society, volume 138 (2016), pages 2548-2551], [S. Harder, Chemical Communications, volume 47 (2011), pages 11945-11947] or [N. Kuhn, Zeitschrift fur Anorganische und Allgemeine Chemie, volume 626 (2000) pages 1387-1392].

[0038] Preferably, in the compound of Formula II, the center R' is H. The compound of Formula II includes the following formula:

[0039] .

[0040] Preferred examples of compounds of Formula II with respect to these formulas are provided in the table below:

[0041]

[0042] The synthesis of some of the compounds of Formula II is described, for example, in the literature [P. Kuo, the European Journal of Inorganic Chemistry, volume 24 (2004), page 4898-4906].

[0043] An example of a compound in which two Rs form a ring together is a compound of the following chemical formula IIc-8 disclosed in KR 2016 / 116 180 A:

[0044] .

[0045] Compounds of chemical formula III include the following chemical formulas:

[0046] .

[0047] Preferably, the compounds of Formula III are compounds of Formulas IIIc, IIIe, IIIf, IIIj, IIIm, IIIp, and IIIq. Preferred examples of compounds of Formula III with respect to these formulas are provided in the table below:

[0048]

[0049]

[0050] Compounds of Chemical Formula IV include the following homoleptic chemical formulas:

[0051] .

[0052] Preferably, the compound of formula IV is the compound of formulas IVcc, IVee, IVff, IVjj, IVmm, IVpp, IVqq.

[0053] Preferred examples of compounds of Formula IV with respect to these formulas are provided in the table below:

[0054]

[0055]

[0056] Some desirable heteroleptic compounds of chemical formula IV are shown below:

[0057]

[0058] .

[0059] Particularly desirable heteroleptic compounds of chemical formula IV are compounds of chemical formulas IVce, IVcf, IVcj, IVcm, IVcp, IVcq, IVef, IVej, IVem, IVep, IVeq, IVfj, IVfm, IVfp, IVfq, IVjm, IVjp, IVjq, and IVpq.

[0060] Synthesis of some of the compounds of Formula IV is described, for example, in the literature [A. Brazeau, Inorganic Chemistry, volume 45 (2006), pages 2276-2281], [B. Nekoueishahraki, Inorganic Chemistry, volume 48 (2009), pages 9174-9179], [R. Duchateau, Chemical Communications, volume 2 (1996), pages 223-224] or [M. Cole, Zeitschrift fur Anorganische und Allgemeine Chemie, volume 641 (2015), pages 2233-2244].

[0061] Compounds of chemical formula V include the following chemical formulas:

[0062] .

[0063] Preferred examples of compounds of Formula V with respect to these formulas are provided in the table below:

[0064]

[0065]

[0066] Compounds of chemical formula VI include the following chemical formulas:

[0067] .

[0068] Regarding these chemical formulas, preferred examples of compounds of chemical formula VI are provided in the table below:

[0069]

[0070]

[0071] In the compound of Formula VII, the central aluminum atom is bonded to two radical monovalent anionic ligands derived from 1,4-diazabutadiene or 1,2,4-triazabutadiene. The compound of Formula VII includes the following formula:

[0072] .

[0073] Preferred examples of compounds of Formula VII with respect to these formulas are provided in the table below:

[0074]

[0075]

[0076] Preferably, R does not have a hydrogen atom at the 1st position, that is, R does not have a hydrogen atom bonded to an atom bonded to a nitrogen or oxygen atom, and thus it is at the beta-position relative to the aluminum atom. Also preferably, R" does not have a hydrogen atom at the 1st position. More preferably, both R and R" do not have a hydrogen at the 1st position. Examples are alkyl groups having two alkyl side groups at the 1st position, namely 1,1-dialkylalkyl, e.g., tert-butyl, 1,1-dimethylpropyl; alkyl groups having two halogens at the 1st position, e.g., trifluoromethyl, trichloromethyl, 1,1-difluoroethyl; trialkylsilyl groups, e.g., trimethylsilyl, triethylsilyl, dimethyl-tert-butylsilyl; aryl groups, in particular phenyl or alkyl-substituted phenyl, e.g., 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl. An alkyl group that does not have a hydrogen atom at position 1 is particularly desirable.

[0077] Compounds of chemical formulas 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 particularly 500 g / mol or less.

[0078] Preferably, the compound of formula I, II, III, IV, V, VI, or VII has a melting point in the range of -80 to 125°C, preferably -60 to 80°C, more preferably -40 to 50°C, particularly -20 to 20°C. It is advantageous for the compound of formula I, II, III, IV, V, VI, or VII to melt to provide a clear liquid, which remains unchanged up to the decomposition temperature.

[0079] Preferably, the compound of formula I, II, III, IV, V, VI, or VII has a decomposition temperature of at least 80°C, more preferably at least 100°C, particularly at least 120°C, e.g., at least 150°C. Often, the decomposition temperature is 250°C or lower. The compound of formula I, II, III, IV, V, VI, or VII has a high vapor pressure. Preferably, the vapor pressure is at least 1 mbar at a temperature of 200°C, more preferably 150°C, particularly 120°C. Generally, the temperature at which the vapor pressure is 1 mbar is at least 50°C.

[0080] The compound of formula I, II, III, IV, V, VI, or VII used in the method according to the present invention is used at a high purity to achieve the best results. High purity means that the material used contains at least 90 weight%, preferably at least 95 weight%, more preferably at least 98 weight%, and particularly at least 99 weight% of a metal or metalloid-containing compound or a compound of formula I, II, III, IV, V, VI, or VII. Purity can be determined by elemental analysis according to DIN 51721 (Prufung fester Brennstoffe - Bestimmung des Gehaltes an Kohlenstoff und Wasserstoff - Verfahren nach Radmacher-Hoverath, August 2001).

[0081] Compounds of formulas I, II, III, IV, V, VI, or VII come into contact with a solid substrate in a gaseous state. For example, they may be heated to a high temperature to be made into a gaseous state. In any case, a temperature below the decomposition temperature of the compound of formulas I, II, III, IV, V, VI, or VII must be selected. The decomposition temperature is the temperature at which the compound of formulas I, II, III, IV, V, VI, or VII in its original state begins to change its chemical structure and composition. Preferably, the heating temperature is in the range of 0°C to 300°C, more preferably 10°C to 250°C, even more preferably 20°C to 200°C, particularly 30°C to 150°C.

[0082] Another method of making 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, the compound of formula I, II, III, IV, V, VI, or VII is typically dissolved in a solvent and sprayed in a carrier gas or under 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 becomes a gaseous state. Various solvents may be used, but the compound of formula I, II, III, IV, V, VI, or VII must exhibit sufficient solubility in said solvent, e.g., at least 1 g / l, preferably at least 10 g / l, more preferably at least 100 g / l. Examples of such solvents are coordinating solvents, such as tetrahydrofuran, dioxane, diethoxyethane, pyridine, or non-coordinating solvents, such as hexane, heptane, benzene, toluene, or xylene. Additionally, solvent mixtures are suitable.

[0083] Alternatively, compounds of formulas I, II, III, IV, V, VI, or VII can be converted to a gaseous state by direct liquid evaporation (DLE), as described, for example, in the literature [J. Yang et al., Journal of Materials Chemistry, 2015]. In this method, compounds of formulas I, II, III, IV, V, VI, or VII are mixed with a solvent, for example, a hydrocarbon, such as tetradecane, and heated below the boiling point of the solvent. By the evaporation of the solvent, compounds of formulas I, II, III, IV, V, VI, or VII become gaseous. This method has the advantage that particulate contaminants are not formed on the surface.

[0084] It is desirable 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 process is generally carried out at a lower heating temperature, which can cause reduced decomposition of the compound of Formula I, II, III, IV, V, VI, or VII. Additionally, it is possible to use increased pressure to push the gaseous compound of Formula I, II, III, IV, V, VI, or VII onto a solid substrate. Often, an inert gas, such as nitrogen or argon, is used as a carrier gas for this purpose. Preferably, the pressure is 10 bar to 10 -7 mbar, more preferably 1 bar to 10 -3 mbar, particularly 1 to 0.01 mbar, e.g. 0.1 mbar.

[0085] Typically, a compound of formulas I, II, III, IV, V, VI, or VII acts as a reducing agent in the process. According to the present invention, a metal or metalloid-containing compound is deposited in a gaseous state on a solid substrate before contacting it with a compound of formulas I, II, III, IV, V, VI, or VII. The metal or metalloid-containing compound is generally reduced to a metal, metal nitride, metal carbide, metal carbonitride, metal alloy, intermetallic compound, or a mixture thereof. In the present invention, the metal film has high electrical conductivity (generally at least 10 4 S / m, preferably at least 10 5 S / m, especially at least 10 6 It is a metal or semimetal-containing film having S / m.

[0086] Compounds of formulas I, II, III, IV, V, VI, or VII have a low tendency to form permanent bonds with the surface of a solid substrate having a deposited metal or metal-containing compound. Consequently, the metal or metal-containing film is hardly contaminated with reaction byproducts of compounds of formulas I, II, III, IV, V, VI, or VII. Preferably, the metal or metal-containing film contains less than 5 weight% of total nitrogen, more preferably less than 1 weight%, particularly less than 0.5 weight%, e.g., less than 0.2 weight%.

[0087] A metal or metalloid-containing compound contains one or more metal or metalloid atoms. 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 positively charged than Cu, and more preferably a metal or metalloid that is more positively charged 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. It is possible to deposit more than one metal or metalloid-containing compound on the surface simultaneously or sequentially. When more than one metal or metalloid-containing compound is deposited on a solid substrate, it is possible for all metal or metalloid-containing compounds to contain the same metal or metalloid or different ones, and preferably, they contain different metals or metalloids.

[0088] Any metal or metalloid-containing compound capable of being in a gaseous state is suitable. These compounds include metal or metalloid alkyls, e.g., dimethyl zinc, trimethylaluminum; metal alkoxylates, e.g., tetramethoxysilicon, tetra-isopropoxyzirconium, or tetra-isopropoxytitanium; metal or metalloid cyclopentadienyl complexes, e.g., pentamethylcyclopentadienyl-trimethoxytitanium or di(ethylcyclopentadienyl)manganese; metal or metalloid carbenes, e.g., tris(neopentyl)neopentylidene tantanrum or biimidazolidinylidene ruthenium chloride; metal or metalloid halides, e.g., aluminum trichloride, tantalum pentachloride, titanium tetrachloride, molybdenum pentachloride, germanium tetrachloride, gallium trichloride, arsenic trichloride, or tungsten hexachloride; It includes carbon monoxide complexes, e.g., hexacarbonyl chromium or tetracarbonyl nickel; amine complexes, e.g., bis(tert-butylimino)bis(dimethylamino)molybdenum, bis(tert-butylimino)bis(dimethylamino)tungsten or tetrakis(dimethylamino)titanium; diketonate complexes, e.g., tris(acetylacetonate)aluminum or bis(2,2,6,6-tetramethyl-3,5-heptaneto)manganese. Metal or metalloid halides, particularly aluminum chloride, aluminum bromide, and aluminum iodide, are preferred. Preferably, the molecular weight of the metal or metalloid-containing compound is 1000 g / mol or less, more preferably 800 g / mol or less, particularly 600 g / mol or less, e.g., 500 g / mol or less.

[0089] The process is preferably performed by an atomic layer deposition (ALD) process. Preferably, the sequence comprising (a) and (b) is performed at least 2 times, more preferably at least 5 times, even more preferably at least 10 times, particularly at least 50 times. Often, the sequence comprising (a) and (b) is performed 1,000 times or less.

[0090] Generally, whenever a solid substrate is exposed to a gaseous metal or metalloid-containing compound or a compound of formulas I, II, III, IV, V, VI, or VII, it is desirable to purge the substrate and surrounding equipment with an inert gas. Preferred examples of inert gases are nitrogen and argon. Purge may take 1 second to 1 minute, preferably 5 seconds to 30 seconds, more preferably 10 seconds to 25 seconds, particularly 15 seconds to 20 seconds.

[0091] Preferably, the temperature of the substrate is 5 to 40°C, for example 20°C, higher than where the metal- or metalloid-containing compound becomes a gaseous state. Preferably, the temperature of the substrate is room temperature to 400°C, more preferably 100 to 300°C, for example 150 to 220°C.

[0092] Preferably, after the deposition of a metal or metal-containing compound on a solid substrate and before contacting the solid substrate having the deposited metal or metal-containing compound with a compound of formulas I, II, III, IV, V, VI, or VII, the solid substrate having the deposited metal or metal-containing compound is brought into contact with a gaseous acid. Without being bound by theory, it is thought that the protonation of the ligands of the metal or metal-containing compound facilitates 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, particularly formic acid.

[0093] Alternatively, it is possible to deposit aluminum from a compound of formulas I, II, III, IV, V, VI, or VII. In this case, the compound of formulas I, II, III, IV, V, VI, or VII is adsorbed onto the surface of a solid substrate, for example, because reactive groups, such as OH groups, are present on the surface of the solid substrate or because the temperature of the solid substrate is sufficiently high. Preferably, the adsorbed compound of formulas I, II, III, IV, V, VI, or VII is decomposed.

[0094] Decomposition can be performed in various ways. The temperature of the solid substrate can be increased above the decomposition temperature. In this case, the process is a chemical vapor deposition (CVD) process. Typically, the solid substrate is heated to a temperature in the range of 300 to 1000°C, preferably in the range of 350 to 600°C.

[0095] In addition, it is possible to expose a compound of formula I, II, III, IV, V, VI, or VII 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 (N2O), nitric oxide (NO), nitrogen dioxide (NO2), or hydrogen peroxide; ammonia or ammonia derivatives, such as tert-butylamine, iso-propylamine, dimethylamine, methylethylamine, or diethylamine; hydrazine or hydrazine derivatives, such as N,N-dimethylhydrazine; a solvent, such as water, alkanes, or tetrachlorocarbons; or a boron compound, such as a boran. The choice depends on the chemical structure of the desired layer. In the case of aluminum oxide, it is preferable to use an oxidizing agent, plasma, or water, particularly oxygen, water, oxygen plasma, or ozone. In the case of aluminum, nitrides, ammonia, hydrazine, hydrazine derivatives, nitrogen plasma, or ammonia plasma are preferred. For aluminum boride, a boron compound is preferred. For aluminum carbide, an alkane or tetrachlorocarbon is preferred. For aluminum carbide nitride, a mixture comprising an alkane, tetrachlorocarbon, ammonia, and / or hydrazine is preferred.

[0096] The process is preferably performed by an atomic layer deposition (ALD) process comprising the following:

[0097] (c) a step of contacting a solid substrate with a compound of formula I, II, III, IV, V, VI or VII, and

[0098] (d) A step of decomposing an adsorbed compound of formula I, II, III, IV, V, VI or VII.

[0099] Preferably, the sequence including (c) and (d) is performed at least 2 times, more preferably at least 5 times, even more preferably at least 10 times, particularly at least 50 times. Often, the sequence including (c) and (d) is performed 1,000 times or less.

[0100] In this case, the temperature of the substrate is preferably 5 to 40°C, for example 20°C, higher than where the metal or metalloid-containing compound becomes a gaseous state. Preferably, the temperature of the substrate is room temperature to 400°C, more preferably 100 to 300°C, for example 150 to 220°C.

[0101] In the method according to the present invention, when the temperature of the substrate is maintained below the decomposition temperature of the metal or metal-containing compound, a single layer is typically deposited on the solid substrate. When molecules of the metal or metal-containing compound are deposited on the solid substrate, the likelihood of additional deposition occurring on top thereof is generally reduced. Accordingly, the deposition of the metal or metal-containing compound on the solid substrate preferably represents a self-limiting process step. A typical layer thickness of the self-limiting deposition process step is 0.01 to 1 nm, preferably 0.02 to 0.5 nm, more preferably 0.03 to 0.4 nm, particularly 0.05 to 0.2 nm. The layer thickness is typically measured by ellipsometry as described in PAS 1022 DE (Referenzverfahren zur Bestimmung von optischen und dielektrischen Materialeigenschaften sowie der Schichtdicke dunner Schichten mittels Ellipsometrie; February 2004).

[0102] Exposure of a substrate to a compound of formula I, II, III, IV, V, VI, or VII or a metal or metal-metal-containing compound may take from milliseconds to several minutes, preferably from 0.1 seconds to 1 minute, particularly from 1 to 10 seconds. The longer the time a solid substrate is exposed to a compound of formula I, II, III, IV, V, VI, or VII or a metal or metal-metal-containing compound at a temperature lower than the decomposition temperature of the compound of formula I, II, III, IV, V, VI, or VII or a metal or metal-metal-containing compound, the more uniform and less defective the formed film is.

[0103] A particular advantage of the method according to the present invention is that compounds of formulas I, II, III, IV, V, VI, or VII are used in a highly versatile manner, and thus process parameters can vary over a wide range. Accordingly, the method according to the present invention includes both a CVD process and an ALD process.

[0104] The method according to the present invention produces an inorganic metal or metal-containing film. The film may be a single monolayer of metal or may be thicker (e.g., 0.1 nm to 1 μm, preferably 0.5 to 50 nm). The film may contain defects, such as holes. However, these defects generally constitute less than half of the surface area covered by the film. The film preferably has a very uniform film thickness, which means that the film thickness at different locations on the substrate varies very little, generally less than 10%, preferably less than 5%. Additionally, the film is preferably a conformal film on the surface of the substrate. Suitable methods for determining film thickness and uniformity are XPS or ellipsometry.

[0105] The film obtained by the method according to the present invention can be used in electronic devices. Electronic devices may have structural features of various sizes (e.g., 1 nm to 100 μm, e.g., 10 nm, 14 nm, or 22 nm). The method for manufacturing the film for electronic devices is particularly suitable for very fine structures. Therefore, electronic devices with a size of less than 1 μm are preferred. Examples of electronic devices are field-effect transistors (FETs), solar cells, light-emitting diodes, sensors, or capacitors. In optical devices, such as light-emitting diodes or photosensors, the film obtained by the method according to the present invention serves to increase the refractive index of the light-reflecting layer.

[0106] A desirable electronic device is a transistor. Preferably, the film acts as a chemical barrier metal in the transistor. A chemical barrier metal is a material that reduces diffusion between adjacent layers while maintaining electrical connections.

[0107] Examples

[0108] Example 1a: 4-(isopropylamino)pent-3-en-2-one( i Synthesis of PrNacacH

[0109] A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in ethanol (100 mL) was added dropwise to a solution of isopropylamine (8.7 mL, 0.1 mol) in ethanol (100 mL). The resulting pale yellow solution was refluxed in a 250 mL round-bottom flask at 100°C for 18 hours. The volume of the dark yellow solution decreased 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.

[0110] 1H 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{ 1 H} NMR (100 MHz, C6D6) δ = 18.59, 24.07, 29.23, 44.69, 95.47, 161.17, 194.26.

[0111] Example 1b: N,N'-Diisopropyl-2,4-Pentanediketimine ( i Synthesis of PrNacNacH

[0112] in dimethyl sulfate (6 mL, 0.063 mol) i A solution of PrNacacH (5.376 g, 0.038 mol) was stirred at ambient temperature for 5 minutes and then left to stand for 24 hours to obtain a viscous orange solution. The color intensity of the solution was increased by the subsequent addition of excess isopropylamine (7 mL, 0.081 mol) and stirring at ambient temperature for 1 hour. An excess mixture of sodium methoxide in methanol (11 mL, 0.048 mol) was added, and the mixture was stirred at ambient temperature for 1 hour. After evaporating the volatile components under reduced pressure, water (40 mL) was added to the resulting product. The contents of the flask were transferred to a separatory funnel. The raw product was extracted with pentane (10 × 40 mL), and the combined organic fractions were dried with anhydrous Na2SO4. The solution was filtered through longitudinally grooved filter paper to obtain a clear solution. Volatile components were removed under reduced pressure i PrNacNacH (2.195 g) was obtained as an orange oil.

[0113] 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).

[0114] 13 C{ 1 H} NMR (100 MHz, C6D6) δ = 19.16, 25.44, 47.35, 94.98,158.33.

[0115] The unprocessed product was used to synthesize an aluminum complex without further purification.

[0116] Example 1c: Synthesis of Compound Ia-1

[0117] A solution of AlCl3 (0.372 g, 2.8 mmol) in diethyl ether (30 mL) was cannulated into a stirred solution of LiAlH4 (0.334 g, 8.4 mmol) in diethyl ether (30 mL) in an ice bath at 0°C. The resulting turbid solution was heated to room temperature and stirred for 40 minutes, after which it was cooled again to -30°C. Subsequently, in diethyl ether (40 mL) i A solution of PrNacNacH (2.035 g, 11.16 mmol) was added dropwise. The resulting mixture was stirred at ambient temperature for 18 hours, after which it was filtered over a crude glass frit using a 2-cm plug of Celite. Diethyl ether was evaporated from the filtrate under reduced pressure to obtain a deep yellow, creamy product. The raw product was purified by sublimation under reduced pressure at 50°C to obtain Compound Ia-1 as pale yellow crystals (1.251 g, 53% yield). mp = 62-63°C.

[0118] 1 H NMR (400 MHz, C6D6) δ = 1.31 (d, 12H), 1.56 (s, 6H), 3.48 (m, 2H), 4.41 (s, 1H).

[0119] 13 C{ 1 H} NMR (100 MHz, C6D6) δ = 21.88, 23.12, 50.59, 97.73, 166.96.

[0120] The results of the heat weight analysis are shown in Figure 1.

[0121] Example 2a: 4-(sec-butylamino)pent-3-en-2-one( s Synthesis of BuNacacH

[0122] A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in ethanol (100 mL) was added dropwise to a solution of sec-butylamine (10 mL, 0.1 mol) in ethanol (100 mL). The resulting pale yellow solution was refluxed in a 250 mL round-bottom flask at 100°C for 18 hours. The volume of the dark yellow solution decreased under reduced pressure. By fractional distillation of the residue at 0.8 Torr at 97°C s BuNacacH was obtained as a pale yellow liquid (14.332 g, 92.3% yield).

[0123] 1 H NMR (400 MHz, 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).

[0124] 13 C{ 1 H} NMR (100 MHz, C6D6) δ = 10.69, 18.86, 21.95, 29.23, 31.12, 50.35, 95.51, 161.63, 194.30.

[0125] Example 2b: N,N'-di(sec-butyl)-2,4-pentanediketimine ( s Synthesis of BuNacNacH

[0126] in dimethyl sulfate (4 mL, 0.043 mol) sA solution of BuNacacH (4.005 g, 0.026 mol) was stirred at ambient temperature for 5 minutes and then left to stand for 24 hours to obtain a viscous orange solution. Subsequently, an excess amount of sec-butylamine (6 mL, 0.059 mol) was added, and the solution was stirred at ambient temperature for an additional 2 hours. An excess mixture of 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 raw product was extracted with pentane (10 × 35 mL), and the combined organic fractions were dried with anhydrous Na2SO4. The solution was filtered through longitudinally grooved filter paper. The remaining solvent was evaporated under reduced pressure to remove the raw s BuNacNacH (5.810 g) was obtained. The raw product was distilled at 0.8 Torr at 85 to 87°C. s BuNacNacH was obtained as a pale yellow liquid (2.405 g, 45% yield).

[0127] 1 H NMR (400 MHz, 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).

[0128] 13 C{ 1 H} NMR (100 MHz, C6D6) δ = 11.15, 19.43, 23.04, 32.54, 52.98, 95.16, 158.67.

[0129] Example 2c: Synthesis of Compound Ia-2

[0130] A solution of AlCl3 (0.381 g, 2.85 mmol) in diethyl ether (30 mL) was cannulated into a stirred solution of LiAlH4 (0.343 g, 8.57 mmol) in diethyl ether (30 mL) in an ice bath at 0°C. The resulting turbid solution was heated to room temperature and stirred for 40 minutes, after which it was cooled again to -30°C. Subsequently, in diethyl ether (40 mL) s A solution of BuNacNacH (2.405 g, 11.43 mmol) was added dropwise. The resulting mixture was stirred at ambient temperature for 18 hours, after which it was filtered over a crude glass frit using a 2-cm plug of Celite. Diethyl ether was evaporated from the filtrate under reduced pressure to obtain a yellow, creamy product. The raw product was purified by sublimation at 0.8 Torr at 45°C to obtain Compound Ia-2 as pale yellow crystals (0.967 g, 35.5% yield). mp = 40°C.

[0131] 1 H NMR (400 MHz, C6D6) δ = 0.83 (6H, 2 CH(CH3) CH2CH3), 1.32 (6H, 2 CH(CH3) CH2CH3), 1.59 (8H, 2 β-C (CH3) + 2 CH(CH3)CHH'CH3), 2.00 (2H, 2 CH(CH3)CHH'CH3), 3.23 (2H, CH (CH3)CH2CH3), 4.50 (1H, α-CH).

[0132] 13 C{ 1 H} NMR (100 MHz, C6D6) δ =12.10, 21.54, 22.46, 30.43, 56.80, 97.91, 167.23.

[0133] The results of the heat weight analysis are shown in Figure 1.

Claims

Claim 1 A method for producing an inorganic film containing a metal or semimetal, comprising: (a) a step of depositing a gaseous metal- or semimetal-containing compound on a solid substrate; and (b) a step of reducing the compound deposited on the solid substrate by contacting it with a gaseous compound of the following chemical formulas I, II, III, IV, V, VI, or VII to produce a film: In the above formula, 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, and R' and R" are hydrogen, an alkyl group, an alkenyl group, an aryl group or a silyl group. Claim 2 The method of claim 1, wherein R is methyl, ethyl, iso-propyl, sec-butyl, tert-butyl, or trimethylsilyl. Claim 3 A method according to claim 1 or 2, wherein R does not have a hydrogen atom at position 1. Claim 4 A method according to claim 1 or 2, wherein the R' at the 3rd position of the ligand of the compound of chemical formula I or II is H. Claim 5 A method according to claim 1 or 2, wherein the metal- or metalloid-containing compound contains Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al or Si. Claim 6 A method according to claim 1 or 2, wherein the metal- or metal-containing compound is a metal or metal halide. Claim 7 A method according to claim 1 or 2, wherein a sequence including (a) and (b) is performed two or more times. Claim 8 A method according to claim 1 or 2, wherein the method is an atomic layer deposition method. Claim 9 A method according to claim 1 or 2, wherein the compound of chemical formula I, II, III, IV, V, VI or VII has a molecular weight of 600 g / mol or less. Claim 10 A method according to claim 1 or 2, wherein a compound of chemical formula I, II, III, IV, V, VI or VII has a vapor pressure of 1 mbar or more at a temperature of 200°C. Claim 11 A method according to claim 1 or 2, wherein the compound of chemical formula I, II, III, IV, V, VI or VII has a melting point of -80 to 125°C. Claim 12 A method according to claim 1 or 2, wherein the inorganic film containing a metal or metalloid contains a metal, metal nitride, metal carbide, metal carbonitride, metal alloy, intermetallic compound, or a mixture thereof. Claim 13 A method according to claim 1 or 2, wherein the inorganic film containing a metal or semimetal contains less than 5 weight percent of nitrogen. Claim 14 A method for using a compound of formulas I, II, III, IV, V, VI, or VII as a reducing agent in a vapor deposition process, the method comprising: (a) a step of depositing a gaseous metal- or metal-containing compound on a solid substrate; and (b) a step of reducing the compound deposited on the solid substrate by contacting it with a gaseous compound of formulas I, II, III, IV, V, VI, or VII to produce a film. In the above formula, 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, and R' and R" are hydrogen, an alkyl group, an alkenyl group, an aryl group or a silyl group. Claim 15 In paragraph 14, a method in which the vapor deposition process is an atomic layer deposition process.

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