CN121127626A - Composition for depositing antimony-containing film and method for manufacturing antimony-containing film by using the same - Google Patents
Composition for depositing antimony-containing film and method for manufacturing antimony-containing film by using the sameInfo
- Publication number
- CN121127626A CN121127626A CN202480029054.2A CN202480029054A CN121127626A CN 121127626 A CN121127626 A CN 121127626A CN 202480029054 A CN202480029054 A CN 202480029054A CN 121127626 A CN121127626 A CN 121127626A
- Authority
- CN
- China
- Prior art keywords
- antimony
- chemical formula
- composition
- thin film
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a composition for depositing an antimony-containing film, which contains an antimony compound that can be effectively used as a precursor of the antimony-containing film, and a method for manufacturing an antimony-containing film by using the same. The antimony compound according to one embodiment is liquid at room temperature and thus has excellent storability and handleability and has high reactivity, thereby being capable of effectively forming a metal thin film.
Description
Technical Field
The present invention relates to a composition for depositing an antimony-containing film, which contains a novel antimony compound as a precursor of the antimony-containing film, and a method for manufacturing an antimony-containing film using the same.
Background
Antimony (Sb) -containing thin films can be used for insulating layers, diffusion preventing layers, hard masks, etch stop layers, seed layers (SEED LAYER), spacers, intermetal dielectric materials and protective film layers, antireflection layers, etc., due to their excellent thin film characteristics, and the application fields are increasingly diversified. In particular, antimony-containing films have excellent etching resistance and are attracting attention as a next-generation material for hard masks for EUV lithography processes.
Meanwhile, semiconductor circuits are miniaturized year by year due to the high performance of devices. Due to miniaturization of semiconductor circuits and increased aspect ratio and diversification of device materials, a technique of forming an ultrafine film having a uniform and small thickness even at low temperature and having excellent electrical characteristics and etching resistance is demanded. However, conventional antimony-containing thin film precursors involve high temperature processes, making it difficult to apply them to plastic substrates, may have reduced thin film deposition rates and thin film purity when the process temperature is reduced, and have limitations of step coverage, etch resistance, and insufficient physical and electrical properties.
Disclosure of Invention
Technical problem
It is an object of the present invention to provide a composition for depositing an antimony-containing film, which can provide an antimony-containing film having excellent quality.
It is another object of the present invention to provide a method for producing an antimony-containing film which allows deposition of a film at a high film deposition rate even under mild reaction conditions and can produce a high-quality antimony-containing film at a high purity.
It is still another object of the present invention to provide an antimony compound having a novel structure, which can be used as a precursor of an antimony-containing thin film.
Technical proposal
In one general aspect, a composition for depositing an antimony-containing film that allows the manufacture of an antimony-containing film having excellent quality includes an antimony compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein R 1 is C1 to C7 alkyl, R 2 is C1 to C7 alkyl or C1 to C7 alkoxy, and A is halogen or C1 to C7 alkoxy.
Preferably, in chemical formula 1, R 1 may be C1 to C5 alkyl, R 2 may be C1 to C5 alkyl or C1 to C5 alkoxy, and A is halogen or C1 to C5 alkoxy.
Preferably, the antimony compound represented by chemical formula 1 may be represented by the following chemical formula 2 or chemical formula 3:
[ chemical formula 2]
[ Chemical formula 3]
Wherein R 1 is C1 to C5 alkyl, R 3 and R 4 are independently of each other C1 to C5 alkyl or C1 to C5 alkoxy, R 5 is C1-C5 alkyl, and X is halogen.
The antimony compound according to one embodiment may be selected from the following compounds, but is not limited thereto:
where Me is methyl, et is ethyl, and Pr is n-propyl or isopropyl.
In another general aspect, a method for manufacturing an antimony-containing film using the above composition for depositing an antimony-containing film is provided.
A method for manufacturing an antimony-containing film according to an embodiment of the present invention may include:
a) Maintaining the temperature of the substrate mounted in the chamber at 30 to 500 ℃, and
B) A composition for depositing an antimony-containing film and a reaction gas according to an embodiment of the present invention are injected into a substrate to form an antimony-containing film.
The reactant gas may include oxygen (O 2), ozone (O 3), oxygen plasma, hydrogen (H 2), hydrogen plasma, water (H 2 O), hydrogen peroxide (H 2O2), nitrogen dioxide (NO 2), nitric Oxide (NO), nitrous oxide (N 2 O), ammonia (NH 3), carbon dioxide (CO 2), formic acid (HCOOH), acetic acid (CH 3 COOH), anhydrous acetic acid ((CH 3CO)2 O), or combinations thereof.
The reaction gas may be supplied after activation by generating plasma at 20W to 1,000W.
In still another general aspect, there is provided a novel compound that can be used as a precursor of an antimony-containing thin film having excellent quality, and the compound may be an antimony compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein R 1 is C1 to C7 alkyl, R 2 is C1 to C7 alkyl or C1 to C7 alkoxy, and A is halogen or C1 to C7 alkoxy, but excluding the case where R 1 is tert-butyl and both R 2 and A are ethoxy.
More preferably, the antimony compound according to one embodiment may be represented by the following chemical formula 2 or chemical formula 3:
[ chemical formula 2]
[ Chemical formula 3]
Wherein R 1 is C1-C5 alkyl, R 3 and R 4 are independently of each other C1-C5 alkyl or C1-C5 alkoxy, R 5 is C1-C5 alkyl, and X is I, but excluding the cases where R 1 is tert-butyl, R 4 is ethoxy and R 5 is ethyl.
Advantageous effects
The composition for depositing an antimony-containing film according to one embodiment of the present invention can be easily stored and handled, allows deposition of a film at a high film deposition rate even under low temperature conditions, and allows manufacture of an antimony-containing film having excellent quality with high purity.
In addition, the composition for depositing an antimony-containing film according to one embodiment of the present invention allows a film having excellent quality to be manufactured in high yield, and thus can be usefully applied to various industrial fields.
In particular, the antimony compound of the present invention has excellent light absorptivity and luminescence effect for EUV, and thus can be very useful as a hard mask or the like used in EUV lithography process.
Drawings
FIG. 1 is a TGA analysis result spectrum of bis (t-butyl) iodoantimony prepared in example 1.
FIG. 2 is a TGA analysis result spectrum of bis (t-butyl) ethoxyantimony prepared in example 2.
FIG. 3 is a TGA analysis result spectrum of (t-butyl) diethoxy antimony prepared in example 3.
Fig. 4 is a result of Scanning Electron Microscope (SEM) analysis of the line/space pattern formed in example 8.
Detailed description of the preferred embodiments
Hereinafter, the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice the same. This invention may, however, be embodied in many different forms and is not limited to the embodiments described herein. Furthermore, it is not intended to limit the scope of protection defined by the claims.
In addition, unless defined otherwise, technical and scientific terms used in the description of the present invention have meanings commonly understood by those skilled in the art, and descriptions of known functions and configurations that obscure the present invention will be omitted in the following description.
Numerical ranges used in this specification include all values within the range including the lower and upper limits, increments by one form logically derived and covering the defined range, all dual limits, and all possible combinations of upper and lower limits in the numerical range defined in different forms. Unless otherwise defined in the specification of the present invention, values that may be outside the numerical range due to experimental errors or rounding of the values are also included in the numerical range defined.
Unless otherwise specifically limited in the present disclosure, "comprising" any element is to be construed as implying that other elements are also included and not excluding any other elements. Furthermore, as used in the specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context indicates otherwise.
The terms "CA to CB" in this specification mean "having a or more and B or less carbon atoms", and the terms "a to B" mean "a or more and B or less".
The term "alkyl" in this specification is a monovalent substituent and includes both linear and branched forms. The alkyl group may have 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms.
As examples, alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and the like, but are not limited thereto.
The term "alkoxy" in this specification is an-O-alkyl group, wherein "alkyl" is as defined above. Specific examples thereof include methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy and the like, but are not limited thereto.
The term "halogen" in the present specification means a group 17 element, and may be any one selected from F, cl, br, and I.
In the present specification, "normal temperature" may refer to a temperature in a state where no artificial temperature adjustment is made, and for example, normal temperature may be 20 to 40 ℃ or 20 to 30 ℃.
Furthermore, when specific manufacturing tolerances and material tolerances are to be indicated in the stated sense, the term "about" in this specification is used in the sense of or near that value and is used to prevent the disclosure of an exact or absolute value being improperly utilized by an unauthorised infringer in order to better understand the specification and appended claims.
Hereinafter, the present invention will be described in detail.
The composition for depositing an antimony-containing film according to an embodiment of the present invention contains a precursor compound having a specific structure, and can provide a high-quality antimony-containing film.
Specifically, the precursor compound according to one embodiment may be an antimony compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein the method comprises the steps of
R 1 is C1 to C7 alkyl, R 2 is C1 to C7 alkyl or C1 to C7 alkoxy, and A is halogen or C1 to C7 alkoxy.
Without being bound by a particular theory, the antimony compound represented by chemical formula 1 exists in a liquid state at normal temperature, and may have excellent reactivity and volatility. Accordingly, the composition for depositing an antimony-containing film according to one embodiment of the present invention can be easily stored and handled, allows deposition of a film at a high film deposition rate even under low temperature conditions, and can provide an antimony-containing film having high purity and excellent durability.
In addition, antimony-containing films made from the composition for depositing antimony-containing films according to one embodiment are very advantageous for forming smaller feature size patterns compared to the chemically amplified resists (CAR, CHEMICALLY AMPLIFIED RESIST) currently in use. Chemically Amplified Resists (CARs) have high sensitivity, but O, F, S and C, which are typical elemental compositions thereof, make the photoresist too transparent at a specific wavelength and thus reduce sensitivity.
Furthermore, chemically Amplified Resists (CARs) can be difficult to pattern due to roughness problems in small feature sizes, and in part due to the nature of the acid catalyzed process, line edge roughness (LER, line edge roughness) increases as the speed of light decreases. However, the antimony compound according to an exemplary embodiment of the present invention has excellent light absorptivity and luminescence effect with EUV, and thus may be very useful as a hard mask used in EUV lithography process.
Specifically, in chemical formula 1 according to an exemplary embodiment of the present invention, R 1 may be a C1 to C7 alkyl group;
R 2 can be C1 to C7 alkyl or C1 to C7 alkoxy, and A can be halogen or C1 to C7 alkoxy. For example, the C1 to C7 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. Preferably, it may be a branched alkyl group, and more preferably, it may be isopropyl, isobutyl, or tert-butyl. Further, the C1 to C7 alkoxy group may be methoxy, ethoxy, propoxy or butoxy, and preferably may be C1 to C3 alkoxy group, and particularly may be methoxy or ethoxy. Halogen may be any one selected from F, cl, br, and I, and may be preferably I.
Furthermore, in chemical formula 1 according to an exemplary embodiment of the present invention, R 1 may be a C1 to C5 alkyl group, R 2 may be a C1 to C5 alkyl group or a C1 to C5 alkoxy group, and a may be a halogen or a C1 to C5 alkoxy group.
As an example, the antimony compound represented by chemical formula 1 may be represented by the following chemical formula 2 or chemical formula 3:
[ chemical formula 2]
[ Chemical formula 3]
Wherein R 1 is C1 to C5 alkyl, R 3 and R 4 are independently of each other C1 to C5 alkyl or C1 to C5 alkoxy, R 5 is C1 to C5 alkyl, and X is halogen.
Specifically, in chemical formulas 2 and 3, the C1 to C5 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. Preferably, it may be a branched alkyl group, and more preferably, it may be isopropyl, isobutyl, or tert-butyl. Further, the C1 to C7 alkoxy group may be methoxy, ethoxy, propoxy or butoxy, and preferably may be C1 to C3 alkoxy group, and particularly may be methoxy or ethoxy. Halogen may be any one selected from F, cl, br, and I, and may be preferably I.
The antimony compound represented by chemical formula 1 may be, for example, selected from the following compounds, but is not limited thereto:
where Me is methyl, et is ethyl, and Pr is n-propyl or isopropyl.
The composition for depositing an antimony-containing thin film according to one embodiment must contain an antimony compound represented by chemical formula 1 as a precursor for depositing a thin film, and the content of the compound represented by chemical formula 1 in the composition may be within a range recognized by those skilled in the art in consideration of film forming conditions of the thin film, thickness of the thin film, characteristics of the thin film, use of the thin film, and the like. In addition, another embodiment of the present invention provides a method for manufacturing an antimony-containing film using the composition for depositing an antimony-containing film.
The method for manufacturing an antimony-containing thin film according to one embodiment allows manufacturing a high quality antimony-containing thin film at a high deposition rate even at a low temperature and low power due to the use of a composition including an antimony compound represented by chemical formula 1 as a precursor. The antimony-containing film may be used for various purposes, for example, an insulating film, an anti-diffusion film, a hard mask, an etch stop layer, a seed layer, a spacer, an anti-reflection layer, an inter-metal dielectric material, and a protective film layer in electronic device manufacturing, and preferably may be used as a hard mask used in an EUV lithography process, but is not limited thereto.
In the method for manufacturing an antimony-containing thin film according to one embodiment, the method for depositing the thin film is not particularly limited as long as it is commonly used in the art, but for example, atomic Layer Deposition (ALD), chemical Vapor Deposition (CVD), metal Organic Chemical Vapor Deposition (MOCVD), low Pressure Chemical Vapor Deposition (LPCVD), plasma Enhanced Chemical Vapor Deposition (PECVD), or Plasma Enhanced Atomic Layer Deposition (PEALD), and in particular, ALD, CVD, or PEALD may be used, but the present invention is not limited thereto.
A method for manufacturing an antimony-containing film according to one embodiment may include:
a) Maintaining the temperature of the substrate mounted in the chamber at 30 to 500 ℃, and
B) A composition for depositing an antimony-containing film and a reaction gas according to an embodiment of the present invention are injected into a substrate to form an antimony-containing film.
The method for manufacturing an antimony-containing film according to one embodiment may further include purging residual deposition components, reaction gases, and byproducts.
Although the substrate is not particularly limited as long as it is commonly used in the art, it may be, for example, a substrate containing one or more semiconductor materials of Si, ge, siGe, gaP, gaAs, siC, siGeC, inAs and InP, a silicon-on-insulator (SOI) substrate, a quartz substrate, a glass substrate for a display, or a flexible plastic substrate such as Polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), and polyester.
In addition, the antimony-containing film may be directly formed on the substrate, but a plurality of conductive layers, dielectric layers, insulating layers, and the like may be further formed between the substrate and the antimony-containing film.
As an example, the temperature of the substrate may be 30 to 500 ℃, 30 to 300 ℃, or 50 to 300 ℃, but is not limited thereto.
As an example, the reaction gas may be supplied after activation by generating plasma at 20W to 1,000W, 20W to 800W, or 50W to 600W.
Specifically, in the method for manufacturing an antimony-containing thin film according to one embodiment, by using the compound of chemical formula 1 as a precursor, a thin film can be efficiently manufactured even in the case of low plasma generation at low temperature.
The reaction gas may remove ligands of the antimony compound contained in the composition for depositing an antimony-containing film to form an antimony-containing atomic layer.
The type of the reaction gas is not particularly limited as long as it is commonly used in the art, but as an example, it may be oxygen gas (O 2), ozone (O 3), oxygen plasma, hydrogen gas (H 2), hydrogen plasma, water (H 2 O), hydrogen peroxide (H 2O2), nitrogen dioxide (NO 2), nitric Oxide (NO), nitrous oxide (N 2 O), ammonia (NH 3), carbon dioxide (CO 2), formic acid (HCOOH), acetic acid (CH 3 COOH), anhydrous acetic acid ((CH 3CO)2 O), or a combination thereof.
As an example, the concentration of ozone in the reaction gas may be 10 g/m 3 to 220 g/m 3, but is not limited thereto.
In the method for manufacturing an antimony-containing thin film according to one embodiment, an inert gas may be used as a transfer gas or a purge gas. The type of the transfer gas or the purge gas is not particularly limited as long as it is generally used in the art, but as an example, it may be argon, nitrogen, krypton, or the like, and may be preferably argon because it is economical.
In the method for manufacturing an antimony-containing thin film according to one embodiment, the deposition conditions may be adjusted according to the desired structure or thermal characteristics of the thin film, and the deposition conditions according to one embodiment may be, for example, an input flow rate of a composition for depositing an antimony-containing thin film including the compound of chemical formula 1, an input flow rate of a reaction gas, a transfer gas, a pressure, RF power, a substrate temperature, or the like. As a non-limiting example, the composition for depositing the antimony-containing film may be input at a flow rate of 10 cc/min to 1000 cc/min, the transfer gas may be 10 cc/min to 1000 cc/min, the reactant gas may be 1 cc/min to 1500 cc/min, the pressure may be 0.5 torr to 10 torr, and the RF power and substrate temperature may be as described above.
In addition, another embodiment of the present invention provides novel compounds that can be used as precursors for antimony-containing films. Specifically, the novel compound may be an antimony compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein R 1 is C1 to C7 alkyl, R 2 is C1 to C7 alkyl or C1 to C7 alkoxy, and A is halogen or C1 to C7 alkoxy. Specifically, in chemical formula 1, the C1 to C7 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, or neopentyl. Preferably, it may be a branched C3 to C5 alkyl group, and more preferably a tert-butyl group. Further, the C1 to C7 alkoxy group may be methoxy, ethoxy, propoxy or butoxy, and may be preferably ethoxy. Halogen may be any one selected from F, cl, br, and I, and may be preferably I. However, the case where R 1 is tert-butyl and both R 2 and a are ethoxy is excluded.
The antimony compound represented by chemical formula 1 may be represented, for example, by the following chemical formula 2 or chemical formula 3:
[ chemical formula 2]
[ Chemical formula 3]
Wherein R 1 is C1 to C5 alkyl, R 3 and R 4 are independently of each other C1 to C5 alkyl or C1 to C5 alkoxy, R 5 is C1 to C5 alkyl, and X is I.
However, the case where R 1 is t-butyl, R 4 is ethoxy, and R 5 is ethyl is excluded.
The antimony compound according to one embodiment of the present invention may be prepared using any method that is feasible to a person skilled in the art.
Hereinafter, the above-described exemplary embodiments will be described in detail by the following examples. However, the following examples are for illustration only and do not limit the scope of the claims.
Hereinafter, the physical properties of the examples were measured as follows:
1) Elemental composition analysis
The elemental composition of the films was analyzed using an X-ray photoelectron spectrometer (K-alpha+, thermoFisher Scientific).
2) Thermogravimetric analysis
Thermogravimetric analysis (TGA, L81-II, LINSEIS) was performed by injecting nitrogen at a pressure of 1.5 bar/min while heating the sample to be analyzed to 500 ℃ at a rate of 10 ℃ per minute.
EXAMPLE 1 preparation of bis (t-butyl) iodoantimony
120 G (0.53 mol) antimony trichloride (SbCl 3) was added to a 10L flask, 3,000 ml of diethyl ether was added thereto, and stirring was performed while maintaining the internal temperature at 10 ℃. To the flask was slowly added 526 ml (1.06 mol) of t-butylmagnesium chloride (2.0M solution in diethyl ether) while maintaining the internal temperature at 10 ℃ and stirring was performed at normal temperature for 4 hours. After the reaction was completed, the residue was removed by a filter, and the solvent and by-products were removed under reduced pressure. Thereafter, purification was performed at a temperature of 42 ℃ and a pressure of 0.4 torr to synthesize 70 g bis (tert-butyl) antimony chloride.
16.7 G (0.11 mol) NaI was added to the 1L flask, 300 ml hexane was added thereto, and stirring was performed while maintaining the internal temperature at 20 ℃. To the flask was added 30 g (0.11 mol) of the prepared bis (t-Butyl) antimony chloride (Sb (t-Butyl) 2 Cl) and stirred at normal temperature for 4 hours to synthesize bis (t-Butyl) iodoantimony. After the completion of the reaction, the residue was removed by a filter, and the solvent and by-products were removed under reduced pressure, thereby obtaining bis (t-butyl) iodoantimony. Thereafter, purification was performed at a temperature of 44 ℃ and a pressure of 0.24 torr to obtain 30 g bis (tert-butyl) antimony iodide.
The TGA analysis result of the bis (t-butyl) iodoantimony prepared in example 1 is shown in fig. 1, and from this it was found that the antimony compound of example 1 had a single evaporation step from about 140 ℃ and the residual mass at 500 ℃ was confirmed to be 23.0%, whereby it was found that the compound was evaporated while exhibiting rapid evaporation characteristics. The results show that the antimony compound of example 1 has excellent thermal stability.
EXAMPLE 2 preparation of bis (t-butyl) ethoxyantimony
5.52 G (0.08 mol) NaOEt was added to a 500 ml flask, 100ml ethanol was added thereto, and stirring was performed while maintaining the internal temperature at 20 ℃. To the flask was added 22 g (0.08 mol) of prepared bis (tert-Butyl) antimony chloride (Sb (t-Butyl) 2 Cl) and stirred at room temperature for 4 hours to synthesize bis (tert-Butyl) ethoxyantimony. After the completion of the reaction, the residue was removed by a filter, and the solvent and by-products were removed under reduced pressure, thereby obtaining bis (t-butyl) ethoxyantimony (13 g). Thereafter, purification was performed at a temperature of 22 ℃ at a pressure of 0.41 torr to obtain 8 g bis (tert-butyl) ethoxyantimony.
The TGA analysis result of the bis (t-butyl) ethoxyantimony prepared in example 2 is shown in fig. 2, and from this, it was found that the antimony compound of example 2 had a single evaporation step from about 70 ℃ and the residual mass at 500 ℃ was confirmed to be 2.9%, thereby finding that the compound was evaporated while exhibiting rapid evaporation characteristics. The results show that the antimony compound of example 2 has excellent thermal stability.
EXAMPLE 3 preparation of t-butyl diethoxy antimony
169 Ml (0.41 mol) of n-butyllithium (2.3M solution in n-hexane) was added to the 500 mL flask, and 300 ml of n-hexane was added thereto with stirring. 19 g (0.41 mol) dimethylamine was slowly added while maintaining the internal temperature of the mixture at-10 ℃, followed by stirring at normal temperature (25 ℃) for 2 hours to synthesize (dimethylamine) lithium.
30 G (0.13 mol) antimony trichloride (SbCl 3) was added to the 1L flask, 300 ml diethyl ether was added thereto, and stirring was performed while maintaining the internal temperature at-10 ℃. To the flask, 21g of the prepared (dimethylamine) lithium was slowly added and stirred at room temperature for 4 hours to synthesize tri-bis methylamino antimony. After synthesis, lithium chloride (LiCl) was removed by a filter, the solvent was removed under vacuum, 300 ml hexane was added, and stirring was performed while maintaining the internal temperature at-20 ℃.
To the flask was slowly added 65 ml (0.13. 0.13 mol) t-butylmagnesium chloride (2.0M solution in diethyl ether) while maintaining the internal temperature at-20 ℃ and stirring was performed at normal temperature for 4 hours. After completion of the reaction, the solvent and byproducts were removed under reduced pressure. Thereafter, purification was performed at a temperature of 30 ℃ and a pressure of 0.4 torr to synthesize 15 g t-butylbis (dimethylamino) antimony.
15.0 G (0.06 mol) t-butylbis (dimethylamino) antimony was added to the 500mL flask, 60 ml hexane was added, and stirring was performed thoroughly. While maintaining the internal temperature of the solution at-40 ℃, 5.18 g (0.12 mol) ethanol was slowly added and stirred at normal temperature for 4 hours to synthesize t-butyl diethoxy antimony. After the completion of the reaction, the residue was removed by a filter, and the solvent and by-products were removed under reduced pressure, thereby obtaining 12 g t-butyldiethoxy antimony.
Thereafter, purification was performed at a temperature of 16 ℃ and a pressure of 0.49 torr to obtain 10 g t-butyldiethoxy antimony.
The TGA analysis result of the t-butyl diethoxy antimony prepared in example 3 is shown in fig. 3, and it was found therefrom that the antimony compound of example 3 had a single evaporation step from about 100 ℃ and the residual mass at 500 ℃ was confirmed to be 5.0%, thereby finding that the compound was evaporated while exhibiting rapid evaporation characteristics. The results show that the antimony compound of example 3 has excellent thermal stability.
Example 4
Antimony oxide films were produced by plasma enhanced atomic layer deposition using the bis (tert-butyl) iodoantimony, bis (tert-butyl) ethoxyantimony, and tert-butyl diethoxyantimony prepared in examples 1 to 3 as antimony precursors.
A silicon substrate is used as a substrate on which an antimony oxide thin film is to be formed, and the silicon substrate is transferred into a deposition chamber in which the temperature is maintained at a certain temperature.
The temperature of the tank of stainless steel material containing the antimony precursor is maintained so that the vapor pressure of the precursor is constant. The vaporized antimony precursor was transferred into the chamber using argon as a transfer gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon. Oxygen is used as the reactive gas and the reaction process is performed using a constant plasma power. In addition, a purge process was performed using argon to remove reaction byproducts. The atomic layer deposition process as described above was set as one cycle, and this specific cycle was repeated to form an antimony oxide thin film, and detailed deposition conditions are shown in table 1 below.
The composition of the deposited antimony oxide film of each precursor under the specific conditions as shown in table 1 was analyzed by an X-ray photoelectron spectrometer, and since carbon and iodine were not detected, it was confirmed that a pure antimony oxide film could be obtained.
TABLE 1
Example 5
Antimony oxide films were produced by atomic layer deposition using the bis (tert-butyl) iodoantimony, bis (tert-butyl) ethoxyantimony, and tert-butyl diethoxyantimony prepared in examples 1 to 3 as antimony precursors.
A silicon substrate is used as a substrate on which an antimony oxide thin film is to be formed, and the silicon substrate is transferred into a deposition chamber in which the temperature is maintained at a certain temperature.
The temperature of the tank of stainless steel material containing the antimony precursor is maintained so that the vapor pressure of the precursor is constant. The vaporized antimony precursor was transferred into the chamber using argon as a transfer gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon. The reaction process is performed using ozone gas of a certain concentration as a reaction gas. In addition, a purge process was performed using argon to remove reaction byproducts. The atomic layer deposition process as described above was set as one cycle, and this specific cycle was repeated to form an antimony oxide thin film, and detailed deposition conditions are shown in table 2 below.
The composition of the deposited antimony oxide film of each precursor under the specific conditions shown in table 2 was analyzed by an X-ray photoelectron spectrometer, and it was confirmed that a pure antimony oxide film could be obtained since carbon and iodine were not detected.
TABLE 2
Example 6
Antimony-containing films were produced by plasma enhanced atomic layer deposition using the bis (tert-butyl) iodoantimony, bis (tert-butyl) ethoxyantimony, and tert-butyl diethoxyantimony prepared in examples 1 to 3 as antimony precursors.
A silicon substrate is used as a substrate on which an antimony-containing thin film is to be formed, and the silicon substrate is transferred into a deposition chamber in which the temperature is maintained at a certain temperature.
The temperature of the tank of stainless steel material containing the antimony precursor is maintained so that the vapor pressure of the precursor is constant. The vaporized antimony precursor was transferred into the chamber using argon as a transfer gas and adsorbed onto the silicon substrate. Thereafter, a purge process was performed using argon. Carbon dioxide gas was used as a reaction gas, and a reaction process was performed using a constant plasma power. In addition, a purge process was performed using argon to remove reaction byproducts. The atomic layer deposition process as described above was set as one cycle, and this specific cycle was repeated to form an antimony-containing thin film, and the detailed deposition conditions are shown in table 3 below.
The composition of the deposited antimony oxide thin film of each precursor under the specific conditions shown in table 3 was analyzed by an X-ray photoelectron spectrometer, and the results are shown in table 4 below. It was determined that films formed from bis (t-butyl) iodoantimony contained carbon and iodine in addition to antimony, and films formed from bis (t-butyl) ethoxyantimony or t-butyl bisethoxyantimony contained carbon in addition to antimony.
TABLE 3
TABLE 4
Example 7
Antimony-containing films were produced by chemical vapor deposition using the bis (tert-butyl) iodoantimony, bis (tert-butyl) ethoxyantimony, and tert-butyl diethoxyantimony prepared in examples 1 to 3 as antimony precursors.
A silicon substrate is used as a substrate on which an antimony-containing thin film is to be formed, and the silicon substrate is transferred into a deposition chamber in which the temperature is maintained at a certain temperature.
The temperature of the bubbler type tank of stainless steel material containing the antimony precursor was maintained so that the vapor pressure of the precursor was constant. The vaporized antimony precursor was transferred into the chamber using argon as the transfer gas. Further, the temperature of the tank of stainless steel material containing water was kept at a constant vapor pressure using water vapor as a reaction gas, and the water vapor was transferred into the chamber using argon gas as a transfer gas. Furthermore, the process pressure is regulated such that the chamber pressure is constantly maintained using a throttle valve. Thus, chemical vapor deposition was performed using an antimony precursor and water vapor to form an antimony-containing film, and detailed deposition conditions are shown in table 5 below.
The composition of the deposited antimony oxide film of each precursor under the specific conditions as shown in table 5 was analyzed by X-ray photoelectron spectroscopy. It was determined that films formed from bis (t-butyl) iodoantimony contained carbon and iodine in addition to antimony, and films formed from bis (t-butyl) ethoxyantimony or t-butyl bisethoxyantimony contained carbon in addition to antimony.
TABLE 5
EXAMPLE 8 patterning of antimony-containing films
An antimony-containing film was formed in the same manner as in example 6 using the bis (tert-butyl) iodoantimony, bis (tert-butyl) ethoxyantimony, and tert-butyl diethoxyantimony prepared in examples 1 to 3 as antimony precursors.
To form 1:1 line-to-space features with a pitch of 24 nm, EUV lithography apparatus is used for patterning with an exposure of 70 mJ/cm 2 to 80 mJ/cm 2. Subsequently, firing was performed at 150 ℃ for 3 minutes, development was performed in 2-heptanone for 15 seconds, and rinsing was performed with the same solvent.
The results of scanning electron microscopic analysis of the line/space pattern formed on the silicon substrate with a pitch of 24 nm are shown in fig. 4, and it was determined that the 1:1 line/space pattern was uniformly formed even at a narrow pitch of 24: 24 nm.
Claims (10)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20230082936 | 2023-06-27 | ||
| KR10-2023-0082936 | 2023-06-27 | ||
| KR1020240082593A KR20250000889A (en) | 2023-06-27 | 2024-06-25 | Composition for depositing antimony-containing thin film and method for manufacturing antimony-containing thin film using the same |
| KR10-2024-0082593 | 2024-06-25 | ||
| PCT/KR2024/008822 WO2025005625A1 (en) | 2023-06-27 | 2024-06-26 | Composition for depositing antimony-containing thin film, and method for manufacturing antimony-containing thin film by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN121127626A true CN121127626A (en) | 2025-12-12 |
Family
ID=93939251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202480029054.2A Pending CN121127626A (en) | 2023-06-27 | 2024-06-26 | Composition for depositing antimony-containing film and method for manufacturing antimony-containing film by using the same |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN121127626A (en) |
| TW (1) | TW202506700A (en) |
| WO (1) | WO2025005625A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960916A (en) * | 1989-09-29 | 1990-10-02 | United States Of America As Represented By The Secretary Of The Navy | Organometallic antimony compounds useful in chemical vapor deposition processes |
| DE102014014036A1 (en) * | 2014-09-26 | 2016-03-31 | Philipps-Universität Marburg | Use of at least one binary group 15 element compound, a 13/15 semiconductor layer and binary group 15 element compounds |
| JP7625723B2 (en) * | 2021-04-23 | 2025-02-03 | インテグリス・インコーポレーテッド | High quantum efficiency dry resist for low dose EUV irradiation |
-
2024
- 2024-06-26 CN CN202480029054.2A patent/CN121127626A/en active Pending
- 2024-06-26 WO PCT/KR2024/008822 patent/WO2025005625A1/en active Pending
- 2024-06-26 TW TW113123820A patent/TW202506700A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202506700A (en) | 2025-02-16 |
| WO2025005625A1 (en) | 2025-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111373072B (en) | Composition for vapor deposition of silicon-containing thin film and method for producing silicon-containing thin film using the same | |
| JP2015073099A (en) | Method for deposition of silicon nitride film | |
| JP6876145B2 (en) | A composition for vapor deposition of a silicon-containing thin film containing a bis (aminosilyl) alkylamine compound, and a method for producing a silicon-containing thin film using the composition. | |
| KR101587509B1 (en) | method of manufacturing a cobalt-containing thin film and a cobalt-containing thin film manufactured thereby | |
| CN115768919B (en) | Vapor deposition precursor compounds and methods of use | |
| CN114644647A (en) | organometallic precursor compounds | |
| CN121127626A (en) | Composition for depositing antimony-containing film and method for manufacturing antimony-containing film by using the same | |
| JP7738107B2 (en) | Composition for vapor deposition of antimony-containing thin films and method for producing antimony-containing thin films using the same | |
| KR102785094B1 (en) | Composition for depositing antimony-containing thin film and method for manufacturing antimony-containing thin film using the same | |
| KR20250000889A (en) | Composition for depositing antimony-containing thin film and method for manufacturing antimony-containing thin film using the same | |
| CN116848288A (en) | High-throughput deposition methods | |
| US12384805B2 (en) | Iodine-containing metal compound and composition for depositing thin film including the same | |
| TWI904406B (en) | Iodine-containing metal compound, composition for depositing thin film including the same and manufacturing method of the same | |
| TWI849615B (en) | Molybdenum compound, preparation method of the same, composition for depositing molybdenum-containing thin film comprising the same, method for producing molybdenum-containing thin film using the composition and molybdenum-containing thin film | |
| TWI882239B (en) | Silicon precursors, their use and process for preparing the same | |
| KR102904483B1 (en) | Novel amino alkoxy silyl amine compound, method for manufacturing thereof and silicon-containing composition for depositing thin film comprising the same | |
| TWI885821B (en) | Cyclodisilazane compound, composition for depositing silicon-containing thin film including the same, and method of manufacturing silicon-containing thin film using the same | |
| TWI870821B (en) | Method for manufacturing an indium-containing thin film using ald | |
| KR20250035633A (en) | Composition for depositing silicon-containing thin film and method for manufacturing a silicon-containing thin film using the same | |
| KR20240170453A (en) | Novel amino alkoxy silyl amine compound, method for manufacturing thereof and silicon-containing composition for depositing thin film comprising the same | |
| JP2024544251A (en) | Molybdenum compound, its manufacturing method, and manufacturing method of thin film containing the same | |
| KR20230102179A (en) | Indium compound, manufacturing method thereof, composition for thin film containing the same, and manufacturing method of indium-containing thin film | |
| KR20160062675A (en) | Nickel Bis beta-ketoiminate precusor and the method for nickel containing film deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |