Method for producing aluminum oxide film

Abstract

The present invention relates to a method for manufacturing an aluminum oxide film on a substrate. The method for manufacturing an aluminum oxide film includes the following steps, a) A step of depositing a compound of general formula (I) or (II) from a gaseous state onto a substrate, [Chemical 1] TIFF2026516328000018.tif3592(where Z is NR2, PR2, OR, SR, CR2, SiR2, X is H or NR’2, n is 1 or 2, R and R’ are an alkyl group, an alkenyl group, an aryl group, or a silyl group) where the temperature of the substrate is 20 to 250 °C, and b) A step of bringing the deposited compound of general formula (I) or (II) into contact with an oxygen-containing decomposition compound in a gaseous state and includes.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing an aluminum oxide film on a substrate, particularly in the field of atomic layer deposition.

Background Art

[0002] As miniaturization progresses in the semiconductor industry, the demand for thin inorganic films on substrates is increasing, while the requirements for the quality of such films are becoming more stringent. Thin aluminum oxide films are used in various applications such as barrier layers and insulators. There are multiple methods known for forming aluminum oxide films. One of them is a method of depositing a film-forming compound on a substrate from a gas phase state. In order to bring metal or metalloid atoms into the gas phase state at an appropriate temperature, it is necessary to provide a volatile precursor, for example, by complexing the metal or metalloid with an appropriate ligand. These precursors need to have sufficient stability for evaporation while having sufficient reactivity to react with the deposition surface.

[0003] Corsino et al. disclose a process for forming an aluminum oxide film using a dimethylaluminum hydride precursor in Journal of Physics D: Applied Physics, Vol. 53 (2020), page 165103. Plasma-enhanced decomposition is required to convert the deposited precursor into an aluminum oxide film. Such harsh conditions are not suitable for all applications. Also, it is difficult to obtain a very high-quality thin film.

[0004] EP 1 788 116 A1 discloses a process for depositing an aluminum film from a dialkylamido dihydroaluminum precursor. However, with this method, films other than aluminum films cannot be obtained.

[0005] S. Buttera et al., in Inorganic Chemistry, Vol. 60 (2021), pp. 11025-11031, disclose a method for using [AlH2(NMe2)]3 to produce aluminum nitride films. Nitrogen plasma was used to obtain the thin films. Such harsh conditions are not suitable for all applications. Furthermore, aluminum oxide films are not mentioned.

[0006] US 2023 / 0 019 365 discloses a method for producing aluminum-containing films using an aluminum-containing film-forming precursor. However, since deposition requires plasma-enhanced decomposition, it may not be suitable for sensitive substrates.

[0007] S. Potts et al. disclosed dimethylaluminum isopropoxide (DMAI) as an aluminum precursor in the Journal of Vacuum Science and Technology A, Vol. 30 (2012), pp. 021505-1 to 021505-12. However, since plasma-enhanced decomposition is required for deposition, it may not be suitable for sensitive substrates. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] EP 1 788 116 A1 [Patent Document 2] US 2023 / 0 019 365 [Non-patent literature]

[0009] [Non-Patent Document 1] Corsino et al., Journal of Physics D: Applied Physics Volume 53 (2020), Page 165103 [Non-Patent Document 2] S. Buttera et al., Inorganic Chemistry, Vol. 60 (2021), pp. 11025-11031. [Non-Patent Document 3] S. Potts et al., Journal of Vacuum Science and Technology A, Vol. 30 (2012), pp. 021505-1 to 021505-12. [Overview of the project] [Problems that the invention aims to solve]

[0010] Therefore, the object of the present invention was to provide a method for producing high-quality aluminum oxide films under mild conditions. In particular, an efficient production method that achieves a high growth rate per cycle was targeted. The materials of the method should be easy to handle and, in particular, required to be vaporizable with minimal decomposition. Furthermore, the materials of the method should not decompose on the deposition surface under the conditions of the method, while having sufficient reactivity to participate in surface reactions. In addition, the method should be versatile and applicable to a variety of substrates. [Means for solving the problem]

[0011] These objectives are as follows: a) A step of depositing a compound of general formula (I) or (II) onto a substrate, [ka] (In the formula, Z is NR2, PR2, OR, SR, CR2, SiR2, X is either H or NR'2, n is either 1 or 2. (R and R' are alkyl groups, alkenyl groups, aryl groups, or silyl groups.) The process involves a substrate temperature of 20 to 250°C, and b) A step of contacting a compound with general formula (I) or (II) with an oxygen-containing decomposition compound. This was achieved by a method for producing an aluminum oxide film, which includes [the specified component].

[0012] In another aspect, the present invention relates to a method for producing an aluminum oxide film, comprising the following steps a) depositing a compound of general formula (I) on a substrate [Chemical formula] (where Z is NR2, PR2, OR, SR, CR2, SiR2, X is H, R' or NR'2, n is 1 or 2, R and R' are an alkyl group, an alkenyl group, an aryl group, or a silyl group), and b) contacting the deposited compound of general formula (I) or (II) with an oxygen-containing decomposition compound

[0013] In another aspect, the present invention relates to a method for producing an aluminum oxide film, comprising the following steps a) depositing a compound of general formula (II) on a substrate [Chemical formula] (where Z is NR2, PR2, OR, SR, CR2, SiR2, X is H, R' or NR'2, n is 1 or 2, R and R' are an alkyl group, an alkenyl group, an aryl group, or a silyl group), and b) contacting the deposited compound of general formula (I) or (II) with an oxygen-containing decomposition compound

[0014] The present invention further relates to the use of a compound of general formula (I) or (II) for producing an aluminum oxide film.

[0015] ​​The present invention further relates to a method for using a compound of general formula (I) or (II) to produce an aluminum oxide film on a substrate, wherein the substrate temperature is 20 to 250°C during deposition. [Modes for carrying out the invention]

[0016] Preferred embodiments of the present invention are described in the specification and claims. Combinations of different embodiments are within the scope of the present invention.

[0017] The method according to the present invention is suitable for producing aluminum oxide films. Aluminum oxide films are inorganic films containing aluminum and oxygen. In the context of the present invention, "inorganic" refers to a material containing at least 5% by mass, preferably at least 10% by mass, more preferably at least 20% by mass, and particularly at least 30% by mass of at least one metal or metalloid. Inorganic films typically contain carbon in the form of a carbide phase including a mixed carbide phase, such as a nitride carbide phase. The carbon content in the inorganic film that is not part of the carbide phase is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly less than 0.2% by mass.

[0018] The aluminum oxide film may contain Al2O3, but may also contain aluminum oxide hydrates, such as AlO(OH) or Al(OH)3. The aluminum oxide is amorphous, partially crystalline, or crystalline, and is preferably amorphous. The aluminum oxide film preferably contains at least 30% by mass, more preferably at least 40% by mass, and particularly at least 45% by mass of aluminum. The aluminum oxide film preferably contains at least 35% by mass, more preferably at least 45% by mass, and particularly at least 50% by mass of oxygen.

[0019] The substrate can be any solid material. These include, for example, metals, metalloids, oxides, nitrides, and polymers. The substrate can also be a mixture of different materials. Examples of metals include aluminum, steel, and copper. Examples of metalloids include silicon, germanium, and gallium arsenide. Examples of oxides include silicon dioxide and titanium dioxide. Examples of nitrides include silicon dioxide, aluminum nitride, titanium nitride, and gallium nitride. Examples of polymers include polyethylene terephthalate (PET), polyethylene naphthalenedicarboxylic acid (PEN), and polyamides.

[0020] The substrate can have any shape. This includes plate-like, film-like, fibrous, particle-like structures of various sizes, and substrates with grooves or other indentations. The size of the substrate is arbitrary. If the substrate has a particle shape, the particle size is from less than 100 nm to several centimeters, preferably in the range of 1 μm to 1 mm. When metal or metalloid-containing compounds are deposited on the substrate, it is desirable to keep the particles or fibers in a fluid state to prevent them from adhering to each other. This can be achieved by stirring, drum rotation, or fluidized bed technology, etc.

[0021] In compounds of general formula (I) or (II), Z is NR2, PR2, OR, SR, CR2, or SiR2, preferably NR2, PR2, OR, or SR, and particularly NR2 or PR2. Z may all be the same or different from each other, preferably the same. X is H, R', or NR'2, where X is H or NR'2, preferably at least one X is H, more preferably at least one X for each Al atom is H, and particularly all X are H, or one X for each Al atom is H and the other X are NR'2 or R'. In the context of the present invention, H is all isotopes of hydrogen, particularly 1 H and 2Contains H. The latter is also called deuterium D. The exponent n is 1 or 2 depending on Z. Usually, when Z is NR2, PR2, OR, SR, n is 2, and when Z is CR2, SiR2... 、 n is 1.

[0022] In compounds of general formula (I) or (II), R and R' are alkyl groups, alkenyl groups, aryl groups, or silyl groups, preferably alkyl groups or silyl groups, particularly methyl, ethyl, isopropyl, sec-butyl, tert-butyl, and trimethylsilyl. R and R' can be the same or different from each other. In many cases, it has been observed that when R and / or R' are different from each other, the melting and / or boiling points of compounds of general formula (I) or (II) decrease, and they become more likely to transition to a gaseous state. Therefore, it is desirable that compounds of general formula (I) or (II) have at least two different R or at least two different R'. The two Rs can form a ring, preferably a 3- to 8-membered ring, particularly a 5- or 6-membered ring.

[0023] Alkyl groups can 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.

[0024] An alkenyl group contains at least one carbon-carbon double bond. This double bond may contain the carbon atom to which R or R' is bonded to the rest of the molecule, or it may be located away from the carbon atom to which R or R' is bonded. Alkenyl groups can be linear or branched. Examples of linear alkenyl groups having a double bond containing the carbon atom to which R or R' is 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 having a double bond located further away from the position where R or 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-hexen-6-yl. Examples of branched alkenyl groups that contain a carbon atom to which the double bond R or R' is bonded to the rest 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 that have a double bond located further away from the position where R' is bonded to the rest of the molecule include 2-methyl-1-buten-4-yl, cyclopenten-3-yl, and cyclohexen-3-yl. Examples of alkenyl groups that have one or more double bonds include 1,3-butadiene-1-yl, 1,3-butadiene-2-yl, and cyclopentadiene-5-yl.

[0025] The aryl group includes aromatic hydrocarbons, such as phenyl, naphthalyl, anthraceneyl, and phenanthreneyl groups, and heteroaromatic groups, such as pyryl, furanyl, thienyl, pyridineyl, quinoyl, benzofluoryl, benzothiophenyl, and thienothienyl. Some of these groups or combinations thereof, such as biphenyl, thienophenyl, or furanylthienyl, are also possible. The aryl group can be substituted with halogens, such as fluorides, chlorides, bromides, and iodides; pseudohalogens, such as cyanides, cyanates, and thiocyanates; alcohols; alkyl chains, or alkoxy chains. Aromatic hydrocarbons are preferred, and phenyl is more preferred.

[0026] A silyl group is a silicon atom that typically has three substituents. Preferably, a silyl group has the formula SiE3, where E is independently of each other a hydrogen atom, an alkyl group, an aryl group, or a silyl group. It is possible for all three E's to be the same, or for two E's to be the same and the remaining E's to be different, or for all three E's to be different, but preferably all E's to be the same. Alkyl and aryl groups 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.

[0027] Preferably, the compound of general formula (I) is one of the following general formulas.

[0028] [ka]

[0029] Preferred examples of compounds of general formula (I) that refer to these general formulas are shown in the table below.

[0030] [Table 1] TIFF2026516328000007.tif250105 TIFF2026516328000008.tif251106 TIFF2026516328000009.tif64111

[0031] Me represents methyl, Et represents ethyl, n-Bu represents n-butyl, -(CH2)2- represents an ethylene group formed by two R atoms, and -(CH2)4- represents a butylene group formed by two R atoms.

[0032] The synthesis method for compounds of general formula (I) is described, for example, by E. Ashby et al. in Inorganic Chemistry, Vol. 10 (1971), pp. 893-899, or by I. Krossing et al. in Zeitschrift fuer Naturforschung B, Vol. 63 (2008), pp. 1045-1051.

[0033] Preferably, the compound of general formula (II) is one of the following general formulas.

[0034] [ka]

[0035] Preferred examples of compounds of general formula (II) that refer to these general formulas are shown in the table below.

[0036] [Table 2] TIFF2026516328000012.tif249106 TIFF2026516328000013.tif249105 TIFF2026516328000014.tif62111

[0037] Me represents methyl, Et represents ethyl, n-Bu represents n-butyl, -(CH2)2- represents an ethylene group formed by two R atoms, and -(CH2)4- represents a butylene group formed by two R atoms.

[0038] The synthesis of several compounds of general formula (II) is described, for example, by K. Ouzounis et al. in Zeitschrift fuer Anorganische und Allgemeine Chemie, Vol. 504 (1983), pp. 67-76, or by A. Storr et al. in Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999), 1972, pp. 326-330.

[0039] Preferably, R does not have a hydrogen atom at position 1, that is, R does not have a hydrogen atom bonded to an atom bonded to a nitrogen or oxygen atom. In this case, the hydrogen atom is at the β position relative to the aluminum atom. Also preferably, R' does not have a hydrogen atom at position 1. Even more preferably, both R and R' do not have a hydrogen atom at position 1. Examples include alkyl groups having two alkyl side chains at position 1, i.e., 1,1-dialkylalkyl groups, e.g., tert-butyl, 1,1-dimethylpropyl; alkyl groups having two halogen atoms at position 1, e.g., trifluoromethyl, trichloromethyl, 1,1-difluoroethyl; trialkylsyl groups, e.g., trimethylsyl, triethylsyl, dimethyl-tert-butylsyl; aryl groups, especially phenyl or alkyl-substituted phenyl, e.g., 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl. Alkyl groups that do not contain a hydrogen atom at position 1 are particularly preferred.

[0040] Compounds of general formula (I) or (II) 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.

[0041] Preferably, the compound of general formula (I) or (II) has a melting point in the range of -80°C to 125°C, preferably -60°C to 80°C, more preferably -40°C to 50°C, and particularly -20°C to 20°C. It is advantageous that the compound of general formula (I) or (II) melts to become a clear liquid without changing at the decomposition temperature.

[0042] Compounds of general formula (I) or (II) 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. Typically, the decomposition temperature is 250°C or lower. Compounds of general formula (I) or (II) have a high vapor pressure. The vapor pressure is preferably at least 1 millibar at 200°C, more preferably 150°C, even more preferably 120°C, particularly at 100°C, for example at 70°C. Typically, the temperature at which the vapor pressure becomes 1 millibar is at least 20°C, for example at 50°C.

[0043] The compound of general formula (I) or (II) used in the method of the present invention is used in high purity to obtain the best results. High purity means that the substance used contains at least 90% by mass, preferably at least 95% by mass, more preferably at least 98% by mass, and particularly preferably at least 99% by mass of the metal or metalloid compound or the compound of general formula (I) or (II). Purity can be determined by elemental analysis in accordance with DIN 51721 (Pruefung fester Brennstoffe-Bestimmung des Gehaltes an Kohlenstoff und Wasserstoff-Verfahren nach Radmacher-Hoverath, August 2001).

[0044] The compound of general formula (I) or (II) is brought into contact with the substrate from a gaseous state. This can be achieved, for example, by heating to a high temperature. In either case, the temperature must be below the decomposition temperature of the compound of general formula (I) or (II). The decomposition temperature is the temperature at which the initial (pristine) compound of general formula (I) or (II) begins to change its 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 particularly 30°C to 150°C.

[0045] Another method for making a compound of general formula (I) or (II) into a gas is direct liquid injection (DLI), as described, for example, in US 2009 / 0 226 612 A1. In this method, the compound of general formula (I) or (II) is typically dissolved in a solvent and sprayed into a carrier gas or vacuum. If the vapor pressure and temperature of the compound of general formula (I) or (II) are sufficiently high and the pressure is sufficiently low, the compound of general formula (I) or (II) will become a gas. A variety of solvents can be used, provided that the compound of general formula (I) or (II) exhibits sufficient solubility in that solvent, for example, at least 1 g / l, preferably at least 10 g / l, and more preferably at least 100 g / l. Examples of these solvents include coordination solvents, such as tetrahydrofuran, dioxane, diethoxyethane, pyridine, or non-coordinating solvents, such as hexane, heptane, benzene, toluene, or xylene. Mixtures of solvents are also suitable.

[0046] Alternatively, compounds of general formula (I) or (II) 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, the compound of general formula (I) or (II) is mixed with a solvent such as a hydrocarbon such as tetradecane, and heated to a temperature below the boiling point of the solvent. The compound of general formula (I) or (II) becomes a gaseous state due to the evaporation of the solvent. This method has the advantage that no particulate impurities are formed on the surface.

[0047] It is preferable to put the compound of general formula (I) or (II) into a gaseous state under reduced pressure. This usually allows the method to be carried out at a lower heating temperature, resulting in reduced decomposition of the compound represented by general formula (I) or (II). It is also possible to push the compound represented by general formula (I) or (II) into the substrate in a gaseous state using pressure. 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 -7 millibars, more preferably 1 to 10 bar -3 Millibars, especially 1 to 0.01 millibars, for example, 0.1 millibar.

[0048] The exposure time of the substrate to the compound of general formula (I) or (II) ranges from milliseconds to several minutes, preferably from 0.1 seconds to 1 minute, and particularly from 1 second to 10 seconds. The longer the exposure time of the substrate to the compound of general formula (I) or (II) at a temperature below the decomposition temperature of the compound, the more regular and less defective the film formed.

[0049] According to the present invention, a deposited compound of general formula (I) or (II) is brought into contact with an oxygen-containing decomposition compound. A suitable oxygen-containing decomposition compound has the ability to react with the compound of general formula (I) or (II) to form aluminum oxide. The oxygen-containing decomposition compound is water, oxygen, or ozone. The oxygen-containing decomposition compound can be applied in its raw state or as a plasma (e.g., oxygen plasma). Preferably, the deposited compound of general formula (I) or (II) is brought into contact with the oxygen-containing decomposition compound in an initial (pristine) state, i.e., without applying a plasma, and the reaction is initiated thermally.

[0050] The oxygen-containing decomposition compound can be converted to a gaseous state in the same manner as the compound of general formula (I) or (II) described above. The oxygen-containing decomposition compound can be converted to a gaseous state by the deposited compound of general formula (I) or (II) at 10 bar to 10 -7 millibars, preferably 1 to 10 bar -3The compounds can be brought into contact at millibars, particularly at partial pressures of 1 to 0.01 millibars, for example, 0.1 millibars. The oxygen-containing decomposition compounds can be brought into contact with the deposited compounds of general formula (I) or (II) as the initial (pristine) compound or as a mixture with an inert gas such as nitrogen or argon.

[0051] The steps of depositing a compound of general formula (I) or (II) and contacting the deposited compound of general formula (I) or (II) with an oxygen-containing decomposition compound can be carried out at the same temperature or different temperatures, but are preferably carried out at the same temperature.

[0052] The deposited compound of general formula (I) or (II) can be brought into contact with the oxygen-containing decomposition compound for a period of milliseconds to several minutes, preferably 0.1 seconds to 1 minute, and particularly 1 second to 10 seconds.

[0053] The method of the present invention may be an atomic layer deposition (ALD) process. Preferably, a series including (a) and (b) is performed at least twice, more preferably at least five times, even more preferably at least ten times, and particularly at least fifty times. Typically, a series including (a) and (b) is not performed more than 1000 times.

[0054] In general, it is preferable to purge the substrate and the surrounding equipment with an inert gas each time the substrate is exposed to a compound of general formula (I) or (II) or a gaseous oxygen-containing decomposition compound. Preferred examples of inert gases are nitrogen and argon. The purging time is 1 second to 1 minute, preferably 5 to 30 seconds, more preferably 10 to 25 seconds, and particularly 15 to 20 seconds.

[0055] Preferably, the substrate temperature is 5°C to 40°C, for example 20°C, higher than the temperature at the location where the compound of general formula (I) or (II) or the oxygen-containing decomposition compound is introduced into a gaseous state. Preferably, the substrate temperature is room temperature or 20°C to 400°C, more preferably 100°C to 300°C, for example 120°C to 250°C or 150°C to 220°C.

[0056] An aluminum oxide film can be obtained by the method of the present invention. The film may be a single molecular layer or may have a thickness of 0.1 nm to 1 μm, preferably 0.5 to 50 nm. The film may contain defects (e.g., pores). However, these defects generally occupy less than half of the surface area covered by the film. It is preferable that the film thickness is very uniform at different locations on the substrate. This means that the variation in film thickness at different locations on the substrate is very small, usually less than 10%, preferably less than 5%. Furthermore, it is preferable that the film is a conformal film on the surface of the substrate. Suitable methods for measuring film thickness and uniformity are XPS or ellipsometry.

[0057] The films obtained by the method of the present invention are used in electronic devices. These electronic devices can have various structural features, for example, 1 nm to 100 μm, such as 10 nm, 14 nm, or 22 nm. The method for forming the films of electronic devices is particularly suitable for forming microstructures. Therefore, electronic components with a size of less than 1 μm are preferred. Examples of electronic devices include field-effect transistors (FETs), charge-trap memory cells, 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 of the present invention play a role in increasing the refractive index of the light-reflecting layer. [Examples]

[0058] Example 1 In an ALD reactor (Plasma Electronic GmbH), a Si wafer with a natural SiOx layer was heated to 180°C. The substrate was brought into contact with the vapor of compound IIa-1, purged with argon for 12 seconds, then brought into contact with water vapor, and purged again with argon for 12 seconds. This series of steps was repeated 100 times. A film with a thickness of 22 nm was obtained, as measured by erythrometry. According to XPS profiling, the bulk composition of this film was 40.8 at% Al and 59.2 at% O.

[0059] Example 2 The procedure of Example 2 was repeated at a reactor temperature of 200°C. A film with a thickness of 21 nm was obtained, as measured by erythrometry. According to XPS profiling, the bulk composition of this film was 40.8 at% Al and 59.2 at% O.

[0060] Example 3 The procedure of Example 1 was repeated using compound Ia-2 instead of compound IIa-1. A film with a thickness of 16 nm and a roughness of 1.4 nm was obtained, as measured by erythrometry. According to XPS profiling, the bulk composition of this film was 40 at% Al and 60 at% O.

[0061] Example 4 The procedure of Example 3 was repeated at a reactor temperature of 200°C. A film with a thickness of 17 nm was obtained, as measured by erythrometry. According to XPS profiling, the bulk composition of this film was 40 at% Al and 60 at% O.

Claims

1. The following steps, a) A step of depositing a compound of general formula (I) or (II) onto a substrate from a gaseous state, 【Chemistry 1】 (In the formula, Z is NR) ２ PR ２ OR, SR, CR ２ , SiR ２ And, X is H or NR' ２ And, n is either 1 or 2, R and R' are alkyl groups, alkenyl groups, aryl groups, or silyl groups. The process involves a substrate temperature of 20 to 250°C, and b) A step of contacting a compound with general formula (I) or (II) deposited with an oxygen-containing decomposition compound in a gaseous state. A method for producing an aluminum oxide film containing [a specific substance].

2. Z is NR ２ PR ２ The method according to claim 1, wherein OR or SR.

3. The method according to claim 1 or 2, wherein at least one X for each Al atom is H.

4. A compound of general formula (I) or (II) is a compound of general formula (Ia) or (IIa), 【Chemistry 2】 The method according to claim 1, wherein R is an alkyl group, an alkenyl group, an aryl group, or a silyl group.

5. The method according to claim 1 or 2, wherein R is methyl, ethyl, isopropyl, sec-butyl, tert-butyl, or trimethylsilyl.

6. The method according to claim 1 or 2, wherein the oxygen-containing decomposition compound is water, oxygen, or ozone.

7. The method according to claim 1 or 2, wherein the series of steps including (a) and (b) are performed at least twice.

8. The method according to claim 1 or 2, wherein the compound of general formula (I) or (II) has a molecular weight of 600 g / mol or less.

9. The method according to claim 1 or 2, wherein the compound of general formula (I) or (II) has a vapor pressure of at least 1 millibar at a temperature of 70°C.

10. The method according to claim 1 or 2, wherein the aluminum oxide film comprises at least 40% by mass of aluminum and at least 45% by mass of oxygen.

11. The method according to claim 1 or 2, wherein the aluminum oxide film is amorphous.

12. Method for using a compound of general formula (I) or (II) to produce an aluminum oxide film. 【Transformation 3】 (where Z is NR ２ , PR ２ , OR, SR, CR ２ , SiR ２ and) X is H or NR' ２ And, n is either 1 or 2, R and R' are alkyl groups, alkenyl groups, aryl groups, or silyl groups.

13. The method of use according to claim 12, wherein the aluminum oxide film is amorphous.

14. The method of use according to claim 12 or 13, wherein the aluminum oxide film has a thickness of 0.5 to 50 nm.

15. The method of use according to claim 12 or 13, wherein the aluminum oxide film is manufactured by atomic layer deposition.

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