Novel aminoalkoxysilylamine compounds, methods for producing the same, and silicon-containing thin film deposition compositions containing the same.

Abstract

The present invention relates to a novel aminoalkoxysilylamine compound, a method for producing the same, a silicon-containing thin film deposition composition containing the same, and a method for producing a silicon-containing thin film using the same. The aminoalkoxysilylamine compound according to the present invention is thermally stable, highly volatile and reactive, and is extremely useful for producing silicon-containing thin films with excellent properties that are stable over a wide temperature range.

Description

[Technical Field]

[0001] The present invention relates to a novel aminoalkoxysilylamine compound, a method for producing the same, a silicon-containing thin film deposition composition containing the same, and a method for producing a silicon-containing thin film using the same. [Background technology]

[0002] Silicon-containing thin films are manufactured in the semiconductor field through various deposition processes in various forms, including silicon films, silicon oxide films, silicon nitride films, silicon carbonitride films, and silicon oxynitride films. In recent years, polycrystalline silicon thin films have been used in thin-film transistors (TFTs) and solar cells, and their application fields are becoming increasingly diverse.

[0003] Known representative techniques for manufacturing silicon-containing thin films include chemical vapor deposition (MOCVD), which involves reacting a mixed gaseous silicon precursor with a reaction gas to form a film on the surface of a substrate, or directly reacting it on the surface to form a film, and atomic layer deposition (ALD), which involves physically or chemically adsorbing a gaseous silicon precursor onto the surface of a substrate and then sequentially introducing a reaction gas to form a film. Various thin film manufacturing technologies, such as low-pressure chemical vapor deposition (LPCVD), which applies these techniques, and chemical vapor deposition (PECVD) and atomic layer deposition (PEALD) that utilize plasma for deposition at low temperatures, are being applied to the manufacturing processes of next-generation semiconductors and display elements. They are used for forming ultrafine patterns and for depositing ultrathin films with nano-scale thickness, uniformity, and excellent properties.

[0004] The precursors used to form silicon-containing thin films are typically compounds in the form of silanes, silane chlorides, aminosilanes, and alkoxysilanes. Specific examples include silane chloride compounds such as dichlorosilane (SiH2Cl2) and hexachlorodisilane (Cl3SiSiCl3), as well as trisilylamine (N(SiH3)3), bis-diethylaminosilane (H2Si(N(CH2CH3)2)2), and di-isopropylaminosilane (H3SiN(i-C3H7)2). These are used in mass production processes for semiconductor and display manufacturing.

[0005] However, due to the miniaturization of devices, the increase in aspect ratio resulting from ultra-high integration, and the diversification of device materials, there is a need for technology to form ultrafine thin films that are uniform, thin, and have excellent electrical properties at desired low temperatures. Conventional silicon precursors have problems with high-temperature processes of over 600°C, step coverage, etching characteristics, and the physical and electrical properties of the thin films. Therefore, there is a need for the development of superior novel silicon precursors. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide novel aminoalkoxysilylamine compounds.

[0007] More specifically, one object of the present invention is to provide a thermally stable and highly volatile aminoalkoxysilylamine compound that is useful as a precursor for the formation of silicon-containing thin films.

[0008] More specifically, one objective of the present invention is to provide a novel aminoalkoxysilylamine compound as a precursor compound that can form a silicon-containing thin film with excellent reactivity and stability over a wide temperature range.

[0009] Furthermore, the present invention provides a method for producing the above-mentioned aminoalkoxysilylamine compounds.

[0010] Furthermore, the present invention provides a silicon-containing thin film deposition composition comprising an aminoalkoxysilylamine compound according to one embodiment of the present invention.

[0011] Furthermore, the present invention provides a method for forming a silicon-containing thin film with excellent properties using a silicon-containing thin film deposition composition containing the above-mentioned aminoalkoxysilylamine compound. [Means for solving the problem]

[0012] The present invention provides an aminoalkoxysilylamine compound represented by the following chemical formula 1.

[0013] [ka] (In the above chemical formula 1, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; A is NR 10 R 11 OR 12 and; R 10 is hydrogen or a C1-C5 alkyl group; R 11 and R 12 Each of these may independently be a C1-C5 alkyl group. However, when A is OR 12 and R1, R8, R9, and R 12 are all ethyl, and R2 to R7 are all methyl, this case is excluded.)

[0014] In a compound according to an embodiment, in Chemical Formula 1, R1 is C1-C3 alkyl; R2, R3, R6, and R7 are each independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; R4, R5, and R8 are each independently hydrogen or C1-C3 alkyl; R9 is C1-C3 alkyl; A is NR 10 R 11 or OR 12 ; R 10 is hydrogen or C1-C3 alkyl; R 11 and R 12 may each independently be C1-C5 alkyl.)

[0015] A compound according to an embodiment may be a compound represented by Chemical Formula 2 below.

[0016]

Chemical Formula

[0017] In a compound according to an embodiment, in Chemical Formula 2, R1 is C1-C3 alkyl; R2, R3, R6, and R7 are each independently hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; R4, R5, R8, and R 10Each is independently hydrogen or a C1-C3 alkyl group; R9 and R 11 This may be a C1-C3 alkyl group.

[0018] The compound according to one embodiment may be a compound represented by the following chemical formula 3.

[0019] [ka] (In the above chemical formula 3, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 and R 12 Each of these may independently be a C1-C5 alkyl group. However, in the above chemical formula 3, R1, R8, R9, and R 12 (Excluding cases where all are ethyl and R2-R7 are all methyl.)

[0020] In one embodiment, the compound in the chemical formula 3 is such that R1 is a C1-C3 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C3 alkyl group; and R9 and R 12 Each of these may independently be a C1-C3 alkyl group.

[0021] The compound according to one embodiment may be at least one selected from the following structures. [ka] [ka] [ka]

[0022] Furthermore, the present invention provides a method for producing an aminoalkoxysilylamine compound of the following chemical formula 1, comprising the step of reacting (C1-C5) alkyllithium, a compound of the following chemical formula 4, and a compound of chemical formula 5 to produce an aminoalkoxysilylamine compound of the following chemical formula 1.

[0023] [ka]

[0024] [ka]

[0025] [ka] (In the above chemical formulas 1, 4, and 5, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; R' is a C1-C5 alkoxy or halogen; A is NR 10 R 11 OR 12 and; R 10 is hydrogen or a C1-C5 alkyl group; R 11 and R 12 Each of these may independently be a C1-C5 alkyl group. However, if A is OR 12 And R1, R8, R9, and R 12 (Excluding cases where all are ethyl and R2-R7 are all methyl.)

[0026] According to one embodiment, the present invention provides a method for producing an aminoalkoxysilylamine compound of chemical formula 1, comprising the step of reacting a compound of the following chemical formula 6 with a halogen source to produce the compound of chemical formula 4, where R' in chemical formula 4 is a halogen.

[0027] [ka] (In the above chemical formula 6, R 1 It is a C1-C5 alkyl group; R 2 and R 3 Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R 21 (It is a C1-C5 alkoxy.)

[0028] Furthermore, the present invention provides a silicon-containing thin film deposition composition comprising a compound represented by the following chemical formula 11.

[0029] [ka] (In the above chemical formula 11, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; A is NR 10 R 11 OR 12 and; R 10 is hydrogen or a C1-C5 alkyl group; R 11 and R 12 Each of these may independently be a C1-C5 alkyl group.

[0030] Furthermore, the present invention provides a method for producing a silicon-containing thin film using a compound represented by the following chemical formula 11.

[0031] [ka] (In the above chemical formula 11, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; A is NR 10 R 11 OR 12 and; R 10 is hydrogen or a C1-C5 alkyl group; R 11 and R 12 Each of these may independently be a C1-C5 alkyl group. [Effects of the Invention]

[0032] The aminoalkoxysilylamine compound according to the present invention is a novel compound that is thermally stable and provides a precursor for a silicon-containing thin film with high volatility, thereby enabling the formation of a silicon-containing thin film with excellent properties.

[0033] Furthermore, the aminoalkoxysilylamine compound according to the present invention can exhibit excellent reactivity over a wide temperature range when used to produce silicon-containing thin films.

[0034] Furthermore, the method for producing an aminoalkoxysilylamine compound according to one embodiment of the present invention can efficiently produce an aminoalkoxysilylamine compound in high yield through a simple process.

[0035] Furthermore, the silicon-containing thin film deposition composition according to one embodiment of the present invention, by containing an aminoalkoxysilylamine compound according to one embodiment of the present invention, can produce a high-quality silicon-containing thin film. [Brief explanation of the drawing]

[0036] [Figure 1] This is a thermogravimetric (TGA) graph of the aminoalkoxysilylamine compound produced in Example 3. [Figure 2] This is a differential scanning calorimetry (DSC) graph of the aminoalkoxysilylamine compound produced in Example 3. [Figure 3] This is the spectral result obtained by analyzing the silicon oxide thin film produced in Example 4 using an infrared spectrometer. [Figure 4] This graph shows the thickness of the thin film deposited per deposition cycle, as analyzed by an ellipsometer, for Example 4, Comparative Example 1, and Comparative Example 2, depending on the substrate temperature. [Figure 5] This figure shows the results of confirming the step coverage of the silicon oxide thin film deposited at a substrate temperature of 200°C in Example 4. [Figure 6] This figure shows the results of confirming the step coverage of the silicon oxide thin film deposited at a substrate temperature of 400°C in Example 4. [Modes for carrying out the invention]

[0037] The present invention will now be described in detail. In this description, unless otherwise defined, the technical and scientific terms used have meanings that are ordinarily understood by a person with ordinary skill in the art to which this invention belongs, and descriptions of prior art functions and structures that may obscure the gist of the present invention in the following description will be omitted.

[0038] The term "C" in this specification A -C B The term "A" means "the number of carbon atoms is between A and B," and the term "A~B" means "A or more and B or less."

[0039] In this specification, the term "alkyl" refers to a monovalent substituted compound, and includes both linear and branched forms.

[0040] The alkyl group may have 1 to 5 carbon atoms, specifically 1 to 3 carbon atoms.

[0041] The alkyl group mentioned above includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, and pentyl as examples.

[0042] In this specification, the term "alkoxy" refers to an -O-alkyl radical, where "alkyl" is defined as above. Specific examples include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, and t-butoxy.

[0043] In this specification, the term "halogen" means an element of Group 17, which may be any one selected from F, Cl, Br, and I.

[0044] Furthermore, the term "includes" in this specification is an open-ended expression equivalent to "equipped with," "contains," "possesses," or "characterizes," and does not exclude any elements, materials, or processes not listed.

[0045] Furthermore, the singular forms used herein are intended to include plural forms unless otherwise specified in the context.

[0046] In this specification, the term "aminoalkoxysilylamine compound" is represented by chemical formula 1 and has the same meaning as the expression "precursor of silicon-containing thin film."

[0047] In this specification, the term "thermal stability" means that the physical properties remain unchanged even during a sustained heating process or high-temperature process, and specifically means that no structural changes occur even when exposed to the harsh conditions described above over a long period of time.

[0048] In this specification, the term "silicon-containing thin film with superior properties" refers to a high-quality silicon-containing thin film with a high silicon content and excellent thermal stability and durability.

[0049] In this specification, "normal temperature" means the temperature when it is not artificially adjusted, and for example, the normal temperature may be 20°C to 40°C, or 20°C to 30°C, or 23°C to 26°C.

[0050] The present invention provides a novel aminoalkoxysilylamine compound useful as a precursor for producing silicon-containing thin films, the aminoalkoxysilylamine compound of the present invention being represented by the following chemical formula 1.

[0051] [ka]

[0052] In the above chemical formula 1, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; A is NR 10 R 11 OR 12 and; R 10 is hydrogen or a C1-C5 alkyl group; R 11 and R 12 Each of these is independently a C1-C5 alkyl group; However, if A is OR 12 And R1, R8, R9, and R 12 Cases where all are ethyl and all of R2-R7 are methyl are excluded.

[0053] The aminoalkoxysilylamine compound of the present invention has a structure in which at least one alkoxy functional group and an amine functional group are introduced together to a silicon atom of a trisilylamine structure. The alkoxy functional group introduced to the silicon atom has an even lower activation energy and improved reactivity, and does not generate non-volatile byproducts, so a high-purity silicon-containing thin film can be easily formed with a high deposition rate.

[0054] The aminoalkoxysilylamine compound according to one embodiment of the present invention can specifically be expressed as an aminosilylalkoxysilylamine compound.

[0055] In one specific example of an aminoalkoxysilylamine compound, in the chemical formula 1, R1 is a C1-C3 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C3 alkyl group; R9 is a C1-C3 alkyl group; and A is NR 10 R 11 OR 12 And; R 10 R is hydrogen or a C1-C3 alkyl group; 11 and R 12 Each of these is independently a C1-C5 alkyl group, and A is OR 12 If so, R1, R8, R9, and R 12 Cases where all are ethyl and all of R2 to R7 are methyl may be excluded.

[0056] Specifically, the aminoalkoxysilylamine compound according to one embodiment of the present invention is one in which A is OR 12 If so, R1, R8, R9, and R 12If all of them are ethyl, they may be excluded.

[0057] As a specific example, the aminoalkoxysilylamine compound of the present invention may be a compound represented by the following chemical formula 2.

[0058] [ka]

[0059] In the aforementioned chemical formula 2, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, R8, and R 10 Each of these is independently either hydrogen or a C1-C5 alkyl group; R9 and R 11 It is a C1-C5 alkyl group.

[0060] In one specific example, the compound in chemical formula 2 has R1 as a C1-C4 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C4 alkyl group, or a C1-C4 alkoxy group; and R4, R5, R8, and R 10 Each is independently hydrogen or a C1-C4 alkyl group; R9 and R 11 This may be a C1-C4 alkyl group.

[0061] More specifically, R1 is a C1-C3 alkyl group; R2, R3, R6, and R7 are independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R4, R5, R8, and R 10 Each is independently hydrogen or a C1-C3 alkyl group; R9 and R 11 This may be a C1-C3 alkyl group.

[0062] As a specific example, the aminoalkoxysilylamine compound of the present invention may be a compound represented by the following chemical formula 3.

[0063] [ka]

[0064] In the aforementioned chemical formula 3, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 and R 12 Each of these is independently a C1-C5 alkyl group.

[0065] However, in the above chemical formula 3, R1, R8, R9, and R 12 Cases where all are ethyl and all of R2-R7 are methyl are excluded.

[0066] In one specific example, the compound in chemical formula 3 is such that R1 is a C1-C4 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C4 alkyl group, or a C1-C4 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C4 alkyl group; and R9 and R 12 Each of these is independently a C1-C4 alkyl group, and R1, R8, R9, and R 12 Cases where all are ethyl and all of R2 to R7 are methyl may be excluded.

[0067] More specifically, R1 is a C1-C3 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C3 alkyl group; R9 and R 12Each of these is independently a C1-C3 alkyl group, and R1, R8, R9, and R 12 Cases where all are ethyl and all of R2 to R7 are methyl may be excluded.

[0068] The aminoalkoxysilylamine compound used in one specific example may be selected from, but is not limited to, the following compounds.

[0069] [ka] [ka] [ka]

[0070] Furthermore, the present invention provides a method for producing the aminoalkoxysilylamine compound.

[0071] As one embodiment, a method for producing an aminoalkoxysilylamine compound of the following chemical formula 1 is provided, which includes the step of reacting (C1-C5) alkyllithium, a compound of the following chemical formula 4, and a compound of chemical formula 5 to produce an aminoalkoxysilylamine compound of the following chemical formula 1.

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] In the aforementioned chemical formulas 1, 4, and 5, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; R' is a C1-C5 alkoxy group or halogen group; and A is NR 10 R 11 OR 12 And; R 10 R is hydrogen or a C1-C5 alkyl group; 11 and R 12 Each of these is independently a C1-C5 alkyl group.

[0076] However, if A is OR 12 And R1, R8, R9, and R 12 Cases where all are ethyl and all of R2-R7 are methyl are excluded.

[0077] Specifically, the method for producing the aminoalkoxysilylamine compound of chemical formula 1 may include the steps of: reacting (C1-C5) alkyllithium with the compound of chemical formula 5 to produce a lithium salt; and reacting the lithium salt with the compound of chemical formula 4 to produce the aminoalkoxysilylamine compound of chemical formula 1.

[0078] As a specific example, the lithium salt may be represented by the following chemical formula 9.

[0079] [ka]

[0080] In the above chemical formula 9, the definition of substituents is the same as in the above chemical formula 5.

[0081] In the method for producing the aminoalkoxysilylamine compound of Chemical Formula 1 according to an embodiment of the present invention, when R' is a halogen in Chemical Formula 4, the compound of Chemical Formula 4 may be produced by including a step of reacting the compound of Chemical Formula 6 with a halogen source to produce the compound of Chemical Formula 4.

[0082]

Chem.

[0083] The halogen source according to an embodiment of the present invention may be any compound that provides a halogen capable of undergoing a substitution reaction with the functional group of Chemical Formula 6. As an example, it may be a compound of Chemical Formula 8 below.

[0084] More specifically, when R' is a halogen in Chemical Formula 4 according to an embodiment of the present invention, the compound may be produced by reacting the compound of Chemical Formula 4 with the compound of Chemical Formula 8 below under the catalyst of Chemical Formula 7 below.

[0085] [Chemical Formula 7] MX 1 3

[0086]

Chem.

[0087] As a specific example, in the chemical formulas 6 to 8, R 1 is C1-C3 alkyl; R 2 and R 3 are each independently C1-C3 alkyl or C1-C3 alkoxy; R 21 is C1-C3 alkoxy; R 22 is C1-C3 alkyl; M is Al; X 1 and X 2 may similarly be Cl to each other.

[0088] In the production method, the alkyllithium is a compound in which lithium is bonded to a C1-C5 alkyl, and specifically, it may be methyllithium, ethyllithium, n-butyllithium, and preferably may be n-butyllithium.

[0089] In the metal halide of the chemical formula 7, the metal of M may be any one metal selected from Group 13 metals, and preferably, the M may be B, Al, or Sn, and the halogens of X 1 and X 2 may be any one halogen selected from F, Cl, Br, and I. More specifically, M may be Al, and X 1 and X 2 may be Cl.

[0090] According to one embodiment, the above reactions may all be carried out in an organic solvent. Specifically, one or a mixture of two or more organic solvents selected from hexane, diethyl ether, toluene, tetrahydrofuran, etc. can be used, but it is not limited thereto.

[0091] Also, the reaction temperature in the reaction may be any temperature usually used in organic synthesis, but it may vary depending on the reaction time, reactants, and the amount of starting materials.

[0092] After the reaction, the purity can be increased by removing by-products through filtration, extraction, recrystallization, distillation, sublimation, chromatography, etc.

[0093] The aminoalkoxysilylamine compounds produced by the above method are thermally stable and highly volatile, making them suitable for forming silicon-containing thin films with excellent properties. Furthermore, they exhibit excellent reactivity over a wide temperature range, enabling the stable production of silicon-containing thin films.

[0094] Furthermore, the present invention provides a silicon-containing thin film deposition composition comprising a compound represented by the following chemical formula 11.

[0095] [ka]

[0096] In the above chemical formula 11, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; and A is NR 10 R 11 OR 12 And; R 10 R is hydrogen or a C1-C5 alkyl group; 11 and R 12 Each of these is independently a C1-C5 alkyl group.

[0097] The aminoalkoxysilylamine compound contained in the silicon-containing thin film deposition composition of the present invention has a structure in which at least one alkoxy functional group and an amine functional group are introduced together to each silicon atom of the trisilylamine structure. The alkoxy functional groups introduced to the silicon atoms have an even lower activation energy and improved reactivity, and do not generate non-volatile byproducts, so that high-purity silicon-containing thin films can be easily formed with a high deposition rate.

[0098] Furthermore, due to its high silicon atom content in the molecule, the silicon-containing thin film deposition composition containing it not only allows for the easy deposition of high-quality silicon-containing thin films with a high deposition rate, but also enables the production of thin films with excellent thermal stability, high durability, and superior purity.

[0099] The silicon-containing thin film deposition composition of the present invention may contain silicon within a content range that can be recognized by those skilled in the art, taking into consideration the thin film deposition conditions, or the thickness and properties of the thin film.

[0100] Furthermore, the present invention provides a method for producing a silicon-containing thin film using an aminoalkoxysilylamine compound represented by the following chemical formula 11.

[0101] [ka]

[0102] In the above chemical formula 11, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 is a C1-C5 alkyl group; and A is NR 10 R 11 OR 12 And; R 10 R is hydrogen or a C1-C5 alkyl group; 11 and R 12 Each of these is independently a C1-C5 alkyl group.

[0103] Specifically, chemical formula 11 in one embodiment of the present invention may be represented by the following chemical formulas 12 or 13.

[0104] [ka]

[0105] In the aforementioned chemical formula 12, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, R8, and R 10 Each of these is independently either hydrogen or a C1-C5 alkyl group; R9 and R 11 It is a C1-C5 alkyl group.

[0106] [ka]

[0107] In the aforementioned chemical formula 13, R1 is a C1-C5 alkyl group; R2, R3, R6, and R7 are each independently hydrogen, a C1-C5 alkyl, or a C1-C5 alkoxy; R4, R5, and R8 are each independently hydrogen or a C1-C5 alkyl group; R9 and R 12 Each of these is independently a C1-C5 alkyl group.

[0108] In one specific example, a method for producing a silicon-containing thin film involves producing a silicon-containing thin film deposition composition containing the thermally stable and highly volatile aminoalkoxysilylamine compound as a precursor, thereby enabling the production of a silicon-containing thin film with excellent properties.

[0109] A specific example of a silicon-containing thin film may be any thin film that can be manufactured within the scope recognized by a person skilled in the art, and specifically, it may be a silicon oxide film (SiO2), a silicon oxycarbide film (SiOC), a silicon nitride film (SiN), a silicon oxynitride film (SiON), a silicon carbonitride film (SiCN), or a silicon carbide film (SiC). In addition, various other high-quality thin films containing silicon can be manufactured within the scope recognized by a person skilled in the art.

[0110] A specific example of a method for manufacturing a silicon-containing thin film may be any method that is possible within the scope of what a person skilled in the art can recognize, and is preferably carried out by atomic layer deposition (ALD), chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). Plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD) is preferred because the deposition of the thin film is easier and the manufactured thin film has excellent properties.

[0111] A specific example of a method for producing a silicon-containing thin film may include the steps of: a) heating and maintaining the temperature of a substrate mounted in a chamber to 30 to 400°C; b) contacting the substrate with an aminoalkoxysilylamine compound according to one specific example, or a silicon-containing thin film deposition composition according to one specific example, and allowing it to be adsorbed onto the substrate; and c) injecting a reaction gas to deposit a silicon-containing thin film onto the substrate.

[0112] Preferably, when producing a silicon-containing thin film according to one specific example of the present invention by plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced chemical vapor deposition (PECVD), the process may further include a step of generating plasma after step a). Also, in step b), the aminoalkoxysilylamine compound according to one specific example, or the silicon-containing thin film deposition composition according to one specific example, may be injected together with the transport gas.

[0113] In one specific example of a method for producing a silicon-containing thin film, the deposition conditions may be adjusted according to the structure or thermal properties of the target thin film. Examples of deposition conditions in one specific example include the input flow rate of the silicon-containing thin film deposition composition containing an aminoalkoxysilylamine compound, the input flow rates of the reaction gas and transport gas, pressure, RF power, and substrate temperature. As a non-limiting example of such deposition conditions, the input flow rate of the silicon-containing thin film deposition composition may be adjusted to 10-1000 cc / min, the transport gas to 10-1000 cc / min, the reaction gas to 1-1000 cc / min, the pressure to 0.5-10 torr, the RF power to 200-1000 W, and the substrate temperature to 30-400°C, preferably 100-350°C, but is not limited thereto.

[0114] In the method for producing a silicon-containing thin film according to one specific example, the reaction gas used may be any gas that is normally used with a silicon precursor, taking into consideration the substance of the silicon-containing thin film to be produced. Specific examples include one or more selected from oxygen (O2), ozone (O3), distilled water (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, diamines, carbon monoxide (CO), carbon dioxide (CO2), saturated or unsaturated hydrocarbons of C1-C12, hydrogen, argon, and helium. The transport gas may be one or more selected from argon, helium, and nitrogen, but is not limited to these.

[0115] The substrate used in the method for manufacturing a silicon-containing thin film according to one specific example may be a substrate containing one or more semiconductor materials from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; an SOI (Silicon On Insulator) substrate; a quartz substrate; or a display glass substrate; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester; but is not limited to these.

[0116] In addition to immediately forming a thin film on the substrate, the silicon-containing thin film may also have a number of conductive layers, dielectric layers, or insulating layers formed between the substrate and the silicon-containing thin film.

[0117] The following describes embodiments of the present invention in detail. However, these are provided so that the invention can be easily implemented by a person with ordinary skill in the art to which the invention pertains, and the invention can be realized in a variety of different forms, and the spirit of the invention is not necessarily limited to these embodiments.

[0118] The structure of the aminoalkoxysilylamine compound according to one embodiment of the present invention is as follows: 1 1H NMR, 13 1C NMR, and 29 Analysis was performed using Si-NMR spectroscopy.

[0119] Furthermore, the thermal stability, volatility, and decomposition temperature of the obtained aminoalkoxysilylamine compounds were measured using thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC).

[0120] Furthermore, the thickness of the thin film according to the embodiment was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE) to determine the thickness of the silicon-containing thin film.

[0121] [Example 1] Synthesis of ((Bis(dimethylamino)(methylsilyl))(methyldimethoxysilyl)amine) [ka] In a flame-dried 4,000 mL flask under an anhydrous and inert atmosphere, (bis(dimethylamino)(methylsilyl))amine (C6H 21 N3Si2) 514g (2.68mol) and hexane (C6H 14 After adding 1,753 mL (13.43 mol), 1,049 mL (2.68 mol) of 2.56 M n-butyllithium (C4H9Li) was slowly added while maintaining the internal temperature at -20°C. After the addition was complete, the mixture was stirred at room temperature for 5 hours, and (bis(dimethylamino)(methylsilyl))amine lithium salt (C6H 21 N3Si2Li) was prepared. Methyltrimethoxysilane (C4H) was added to a flame-dried 5,000 mL flask under anhydrous and inert atmosphere. 12 O3Si) 365.78g (2.68mol) and hexane (C6H 14 ) 1,000 mL (11.60 mol) was heated while maintaining the internal temperature at -20°C (bis(dimethylamino)(methylsilyl))amine lithium salt (C6H 21After slowly adding the mixture to N3Si2Li, the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the reaction mixture was filtered to remove the methoxylithium salt (LiOCH3). The solvent was then removed from the resulting filtrate under reduced pressure, and the compound was distilled under reduced pressure at 72°C @ 1 torr to obtain 348 g (1.17 mol) of the title compound, (bis(dimethylamino)(methylsilyl))(methyldimethoxysilyl)amine. (Yield 43.8%) 1 H-NMR(C6D6):δ 0.20(s,3H Si(CH3)((OCH3)2)0.34(m,6H,(SiHN((CH3)2CH3)2,2.49(d,12H(Si-N((CH3)2) 2, ,3.35(s,6H,(Si-OCH3)2),4.78(m,2H,(Si-H)2 29 Si-NMR(C6D6):δ -18.19(SiH(CH3)(N((CH3)2)2,-18.60(Si(CH3)((OCH3)2) 13 C-NMR(C6D6):δ 49.49(Si(CH3)((OCH3)2),38.22(SiH(CH3)(N((CH3)2)2, -0.83(Si(CH3)((OCH3)2),-4.17(SiH(CH3)(N((CH3)2)2

[0122] [Example 2] Synthesis of (Bis(dimethylamino)(methylsilyl))(methylmethoxysilyl)amine [ka] In a flame-dried 4,000 mL flask under an anhydrous and inert atmosphere, (bis(dimethylamino)(methylsilyl))amine (C6H 21 N3Si2) 269g (1.40mol) and hexane (C6H 14After adding 917 mL (7.02 mol), 549 ml (1.40 mol) of 2.56 M n-butyllithium (C4H9Li) was slowly added while maintaining the internal temperature at -20°C. After the addition was complete, the mixture was stirred at room temperature for 5 hours, and (bis(dimethylamino)(methylsilyl))amine lithium salt (C6H 21 N3Si2Li) was prepared. Methyl dimethoxysilane (C3H) was added to a flame-dried 5,000 mL flask under anhydrous and inert atmosphere. 10 O2Si) 149.24g (1.40mol) and hexane (C6H 14 ) 1,000 mL (11.60 mol) was heated while maintaining the internal temperature at -20°C (bis(dimethylamino)(methylsilyl))amine lithium salt (C6H 21 After slowly adding the mixture to N3Si2Li, the mixture was stirred at room temperature for 5 hours. After the reaction was complete, the reaction mixture was filtered to remove the methoxylithium salt (LiOCH3), and the solvent was removed from the resulting filtrate under reduced pressure. The mixture was then distilled under reduced pressure at 84°C @ 5.4 torr to obtain 180 g (0.677 mol) of the title compound, (bis(dimethylamino)(methylsilyl))(methylmethoxysilyl)amine. (Yield 48.2%) 1 H-NMR(C6D6):δ 0.22(d,3H Si(CH3)H((OCH3)),0.28(m,6H,(SiHN((CH3)2CH3)2, 2.46(d,12H(Si-N((CH3)2)2,3.36(s,3H,(Si(CH3)H((OCH3))),4.57(m,3H Si(CH3)H((OCH3)),4.78(m,2H,(SiHN((CH3)2CH3)2 29 Si-NMR(C6D6):δ -17.43(SiH(CH3)(N((CH3)2)2,-31.68(Si(CH3)H((OCH3))

[0123] [Example 3] Synthesis of (Bis(dimethylamino)(dimethylsilyl))(methyldimethoxysilyl)amine [ka] In a flame-dried 250 mL flask under anhydrous and inert atmosphere, methyltrimethoxysilane (C4H 12 After adding 50 g (0.36 mol) of O3Si and 0.1 g (0.005 mol) of aluminum chloride (AlCl3), 34.57 g (0.44 mol) of acetyl chloride (CH3COCl) was slowly added while maintaining the internal temperature at room temperature, and the mixture was stirred at 55°C for 24 hours. After the reaction was complete, the reaction mixture was filtered to remove aluminum chloride (AlCl3), and methyl acetate (CH3COOCH3), which was produced after the reaction, was removed from the resulting filtrate under reduced pressure to produce chlorodimethoxymethylsilane (C3H9ClO2Si).

[0124] Bis(dimethylamino)dimethylsilylamine (C8H 25 N3Si2) 10g (0.045mol) in hexane (C6H 14 After adding 30 mL (0.22 mol), 2.56 M n-butyllithium (C4H9Li) was slowly added at -20°C. After stirring at room temperature for 5 hours, bis(dimethylamino)dimethylsilylamine lithium salt (C8H 24 N3Si2Li) was prepared. The chlorodimethoxymethylsilane (C3H9ClO2Si) prepared above was mixed with hexane (C6H 14 After adding 30 mL (0.22 mol) of bis(dimethylamino)dimethylsilylamine lithium salt (C8H) while maintaining the internal temperature at -20°C 24After slowly adding N3Si2Li), the mixture was stirred at room temperature for 5 hours. After the reaction was complete, the reaction mixture was filtered to remove lithium chloride (LiCl), and the solvent was removed from the resulting filtrate under reduced pressure to obtain the title compound (bis(dimethylamino)(dimethylsilyl))(methyldimethoxysilyl))amine (CH3Si(CH3O)2N(Si(CH3)2(NCH3)2)2) 9.5 g (0.029 mol) (yield 68%). 1 H-NMR(C6D6):δ 0.20(s,3H CH3Si(CH3O)2),δ 0.30(s,12H N(Si(CH3)2N(CH3)2)2),2.44(s,12H N(Si(CH3)2N(CH3)2)2),3.33(s,6H CH3Si(CH3O)2) 29 Si-NMR(C6D6):δ -5.35(N(Si(CH3)2N(CH3)2)2,-27.90 CH3Si(CH3O)2

[0125] [Example 4] Fabrication of silicon oxide thin film by plasma-enhanced atomic layer deposition (PEALD) Using a conventional plasma-enhanced atomic layer deposition (PEALD) apparatus employing a known plasma-enhanced atomic layer deposition (PEALD) method, the aminoalkoxysilylamine compound produced in Example 3 was used as a precursor to form a silicon oxide thin film, and the deposition of the silicon oxide film was evaluated.

[0126] A silicon substrate was used as the substrate on which the silicon oxide thin film was to be formed. The silicon substrate was transferred into a deposition chamber and maintained at a constant temperature as shown in Table 1 below.

[0127] A stainless steel bubbler-type canister filled with the precursor was maintained at the temperature shown in Table 1 below, so that the vapor pressure of the precursor remained constant. The vaporized precursor was transferred into the chamber using argon gas as the transfer gas and deposited onto a silicon substrate.

[0128] Specifically, the silicon substrate was maintained at 200°C, and the precursor from Example 3 was filled into a stainless steel bubbler container and maintained at 83°C. Argon was used as the reaction gas along with oxygen, and the inert gas argon was used for purging. Below, Table 1 shows the specific method for depositing silicon oxide thin films.

[0129] [Table 1]

[0130] The thickness of the deposited thin film was measured using an ellipsometer (UV Spectroscopic Ellipsometer, Elli-SEU-am12, Ellipso Technology), the formation of the silicon oxide thin film was analyzed using an infrared spectrophotometer (Fourier transform infrared, VERTEX 70v, Bruker), and the composition of the silicon oxide thin film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific). In addition, the step coverage of the silicon oxide thin film was confirmed using a transmission electron microscope (Tecnai F-30 S-Twin, FEI).

[0131] [Comparative Example 1] Production of silicon oxide thin film by plasma-enhanced atomic layer deposition (PEALD) In forming a silicon oxide thin film using the same method as described in Example 4, a diisopropylaminosilane precursor was used as a precursor, cooled to 11°C, instead of the aminoalkoxysilylamine compound produced in Example 3. The silicon substrate was kept at a temperature of 50-200°C during the experiment. The thickness of the deposited thin film was measured using an ellipsometer (UV Spectroscopic Ellipsometer, Elli-SEU-am12, Ellipso Technology), and the composition of the silicon oxide thin film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific).

[0132] [Comparative Example 2] Production of silicon oxide thin film by plasma-enhanced atomic layer deposition (PEALD) In forming a silicon oxide thin film using the same method as described in Example 4, instead of the aminoalkoxysilylamine compound produced in Example 3, a bisquarylbutylaminosilane precursor was heated to 41°C and used as a precursor, and the silicon substrate was heated in the range of 50 to 200°C for the experiment. The thickness of the deposited thin film was measured using an ellipsometer (UV Spectroscopic Ellipsometer, Elli-SEU-am12, Ellipso Technology), and the composition of the silicon oxide thin film was analyzed using an X-ray photoelectron spectrometer (K-Alpha+, ThermoFisher Scientific).

[0133] Figure 3 shows the spectral results obtained by analyzing the thin film deposited in Example 4 using an infrared spectrometer, at a wavenumber of 1060 cm⁻¹. -1 This shows that the Si-O bond was accurately represented.

[0134] Figure 4 is a graph showing the thickness of the thin film deposited per cycle as a function of substrate temperature, obtained by analyzing the thin films of Example 4, Comparative Example 1, and Comparative Example 2 using an ellipsometer. The aminoalkoxysilylamine compound precursor of Example 4 was found to have an atomic layer deposition (ALD) window at silicon substrate temperatures of 100-200°C and above 400°C. In contrast, Comparative Examples 1 and 2, which used diisopropylaminosilane and bisquaritbutylaminosilane precursors, showed no atomic layer deposition window from 50-200°C, with the thickness of the thin film deposited per cycle decreasing as the substrate temperature increased. Furthermore, under the same conditions, Example 4 showed a higher thickness of the thin film deposited per cycle compared to Comparative Examples 1 and 2, suggesting it can be a favorable precursor in processes requiring high throughput.

[0135] Table 2 below shows the results of analyzing the composition and impurities of the deposited thin films using an X-ray photoelectron spectrometer. The thin films deposited in Example 4, Comparative Example 1, and Comparative Example 2 were all found to be free of carbon and nitrogen impurities. At the same silicon substrate temperature of 100°C, the O / Si ratio of Example 4 was 1.99, forming an ideal SiO2 thin film, while Comparative Examples 1 and 2 had ratios of 2.04 and 2.08, respectively, and were analyzed as thin films containing a large amount of oxygen.

[0136] [Table 2]

[0137] Figures 5 and 6 show the results of transmission electron microscopy analysis performed to observe the step coverage of thin films manufactured at substrate temperatures of 200°C and 400°C in Example 4. For a pattern substrate with an aspect ratio of 14, the step coverage was 101% and 97% relative to the lower wall, demonstrating excellent step coverage.

[0138] Figures 1 and 2 confirm the high volatility, stability, and thermal decomposition properties of the aminoalkoxysilylamine compound precursors produced in Examples 1-3.

[0139] Furthermore, as can be seen from Table 2, Figures 3, 4, 5, and 6, when the aminoalkoxysilylamine compound according to the embodiment of the present invention is used as a precursor for thin film deposition, it is possible to produce silicon-containing thin films with the desired excellent properties in a high processing rate, and the produced silicon-containing thin films have excellent step coating properties.

[0140] Although specific parts of the present invention have been described in detail above, it will be clear to those with ordinary skill in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the invention. Therefore, the substantial scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An aminoalkoxysilylamine compound represented by the following chemical formula 1. 【Chemistry 1】 (In the above chemical formula 1, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ is C1-C5 alkyl; A is NR １０ R １１ OR １２ And; R １０ is hydrogen or a C1-C5 alkyl group; R １１ and R １２ Each of these is independently a C1-C5 alkyl group; However, if A is OR １２ And R １ , R ８ , R ９ , and R １２ All of them are ethyl, R ２ ~R ７ (Except in cases where all of them are methyl.)

2. The aforementioned R １ It is a C1-C3 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C3 alkyl group; R ９ It is a C1-C3 alkyl group; A is NR １０ R １１ OR １２ And; R １０ is hydrogen or a C1-C3 alkyl group; R １１ and R １２ Each of these is independently a C1-C5 alkyl group, The above A is OR １２ And R １ , R ８ , R ９ , and R １２ The aminoalkoxysilylamine compound according to claim 1, excluding the case where all of them are ethyl.

3. The aminoalkoxysilylamine compound according to claim 1, which is represented by the following chemical formula 2 or chemical formula 3. 【Chemistry 2】 (In the above chemical formula 2, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , R ８ , and R １０ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ and R １１ (It is a C1-C5 alkyl group.) 【Transformation 3】 (In the above chemical formula 3, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ and R １２ Each of these is independently a C1-C5 alkyl group. However, in the above chemical formula 3, R １ , R ８ , R ９ , and R １２ All of them are ethyl, R ２ ~R ７ (Except in cases where all of them are methyl.)

4. R １ It is a C1-C3 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C3 alkyl group, or a C1-C3 alkoxy group; R ４ , R ５ , R ８ , and R １０ Each is independently either hydrogen or a C1-C3 alkyl group; R ９ , R １１ and R １２ The aminoalkoxysilylamine compound according to claim 3, wherein each of the members is independently a C1-C3 alkyl group.

5. The aminoalkoxysilylamine compound according to claim 1, which is selected from the following compounds. 【Chemistry 4】 【Transformation 5】 【Transformation 6】

6. A method for producing an aminoalkoxysilylamine compound of the chemical formula 1, comprising the step of reacting (C1-C5) alkyllithium, a compound of the chemical formula 4 below, and a compound of the chemical formula 5 to produce an aminoalkoxysilylamine compound of the chemical formula 1 below. 【Transformation 7】 【Transformation 8】 【Chemistry 9】 (In the above chemical formulas 1, 4, and 5, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ is C1-C5 alkyl; R' is a C1-C5 alkoxy or halogen; A is NR １０ R １１ OR １２ And; R １０ is hydrogen or a C1-C5 alkyl group; R １１ and R １２ Each of these is independently a C1-C5 alkyl group; However, when A is OR １２ and R １ , R ８ , R ９ , and R １２ are all ethyl and R ２ to R ７ are all methyl, it shall be excluded.)

7. A method for producing the aminoalkoxysilylamine compound of chemical formula 1 according to claim 6, wherein, in the chemical formula 4, R' is a halogen, the method further comprises the step of reacting the compound of chemical formula 6 below with a halogen source to produce the compound of chemical formula 4. 【Chemistry 10】 (In the above chemical formula 6, R １ It is a C1-C5 alkyl group; R ２ and R ３ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ２１ (It is a C1-C5 alkoxy.)

8. A silicon-containing thin film deposition composition comprising an aminoalkoxysilylamine compound represented by the following chemical formula 11. 【Chemistry 11】 (In the above chemical formula 11, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ It is a C1-C5 alkyl group; A is NR １０ R １１ OR １２ And; R １０ is hydrogen or a C1-C5 alkyl group; R １１ and R １２ These are each independently C1-C5 alkyl groups.

9. A method for producing a silicon-containing thin film using an aminoalkoxysilylamine compound represented by the following chemical formula 11. 【Chemistry 12】 (In the above chemical formula 11, R １ It is a C1-C5 alkyl group; R ２ , R ３ , R ６ , and R ７ Each of these is independently hydrogen, a C1-C5 alkyl group, or a C1-C5 alkoxy group; R ４ , R ５ , and R ８ Each is independently either hydrogen or a C1-C5 alkyl group; R ９ It is a C1-C5 alkyl group; A is NR １０ R １１ OR １２ And; R １０ is hydrogen or a C1-C5 alkyl group; R １１ and R １２ These are each independently C1-C5 alkyl groups.

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