WO2018182307A1 - Silicon nitride film etching composition - Google Patents

Silicon nitride film etching composition Download PDF

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Publication number
WO2018182307A1
WO2018182307A1 PCT/KR2018/003652 KR2018003652W WO2018182307A1 WO 2018182307 A1 WO2018182307 A1 WO 2018182307A1 KR 2018003652 W KR2018003652 W KR 2018003652W WO 2018182307 A1 WO2018182307 A1 WO 2018182307A1
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Prior art keywords
carbon atoms
integer
nitride film
silicon nitride
independently
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PCT/KR2018/003652
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French (fr)
Korean (ko)
Inventor
김동현
박현우
이명호
송명근
정진배
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주식회사 이엔에프테크놀로지
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Priority claimed from KR1020180035221A external-priority patent/KR102240647B1/en
Priority claimed from KR1020180035260A external-priority patent/KR102240654B1/en
Application filed by 주식회사 이엔에프테크놀로지 filed Critical 주식회사 이엔에프테크놀로지
Publication of WO2018182307A1 publication Critical patent/WO2018182307A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material

Definitions

  • the present invention relates to a silicon nitride film etching composition which minimizes an etching rate for a silicon oxide film, selectively etches a silicon nitride film, particles do not remain on a substrate, and is stable at high temperatures.
  • Silicon oxide film (SiO2) and silicon nitride film (SiNx) are used as representative insulating films used in semiconductor manufacturing processes, and may be used alone, or one or more layers of silicon oxide and one or more layers of silicon nitride are alternately stacked.
  • the silicon oxide film and the silicon nitride film are also used as a hard mask for forming a conductive pattern such as a metal wiring.
  • the wet etching process of the silicon nitride film generally uses a mixture of phosphoric acid and deionized water at a high temperature of about 160 ° C., but adds silicon-based additives for the purpose of preventing etching of the silicon oxide film due to phosphoric acid in the high temperature etching process.
  • One etching composition has been proposed.
  • silicic acid or silicate may cause particles that may affect the substrate, and thus may not be suitable for a semiconductor manufacturing process.
  • Korean Patent Laid-Open Nos. 2011-0037741 and 2011-0037766 an oxime silane and an alkoxysilane compound were added to phosphoric acid to control the etching rate of the silicon oxide film to 1 ⁇ / min or less, and a fluorine compound was added to the nitride film etch rate. It is starting to raise.
  • the conventional silane compound has a problem in that a polymer siloxane compound (Si-O-Si) is formed upon contact with water and foreign matters adhere to the wafer surface, and the etching rate of the silicon nitride film and the oxide film due to the loss of the silicon compound is uniform. Problems arise.
  • particles are induced due to stability problems of the silicon additives included in the conventional etching composition, causing many problems in the semiconductor manufacturing process.
  • the present invention can selectively etch a silicon nitride film while minimizing the etching of the silicon oxide film, and an object of the present invention is to provide a high selectivity silicon nitride film etching composition that does not have problems such as generation of particles affecting semiconductor device characteristics.
  • the present invention is phosphoric acid; And a silicon-based compound represented by Formula 1 below.
  • R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or ego;
  • L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
  • L 3 is cycloalkylene having 3 to 8 carbon atoms
  • Q is -O- or -N [(CH 2 CH 2 O) y -R 12 ]-;
  • A is -O- or -N [(CH 2 CH 2 O) z -R 13 ]-;
  • R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer of 0 to 5
  • L may be the same or different from each other
  • A may be the same or different from each other
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • y and z are each independently an integer from 0 to 20;
  • L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • a ' is -O- or -N [(CH 2 CH 2 O) d -R 23 ]-;
  • R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • a is an integer of 0 to 5
  • L ' may be the same or different from each other
  • A' may be the same or different from each other
  • b, c and d are each independently an integer of 0 to 20.
  • the silicon-based compound may be a silicon-based compound represented by the following formula (2) or (3).
  • R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or ego;
  • L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
  • L 3 is cycloalkylene having 3 to 8 carbon atoms
  • R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer of 0 to 5
  • L may be the same or different from each other
  • A may be the same or different from each other
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • y and z are each independently an integer from 0 to 20;
  • L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • a is an integer of 0 to 5
  • L ' may be the same or different from each other
  • A' may be the same or different from each other
  • b, c and d are each independently an integer of 0 to 20.
  • the silicon-based compound may be a silicon-based compound represented by the following formula (4) or (5).
  • R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or ego;
  • L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
  • L 3 is a cycloalkylene having 3 to 8 carbon atoms
  • R 11 is hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 10 carbon atoms;
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • L 1 ′ and L 2 ′ are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 31 and R 32 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • b is an integer of 0-20.
  • each of R 1 to R 3 of the silicon compound of Formula 4 or 5 is independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms;
  • L 1 and L 2 are each independently alkylene having 1 to 7 carbon atoms, cycloalkylene having 5 to 7 carbon atoms, or — (CH 2 ) x —L 3 —;
  • L 3 is cycloalkylene having 5 to 7 carbon atoms;
  • R 11 is hydrogen or alkyl of 1 to 7 carbon atoms;
  • n is an integer from 1 to 10;
  • x can be an integer from 2 to 7.
  • the silicon-based compound may be a silicon-based compound represented by the following formula (6), (7) or (8).
  • R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or ego;
  • L 1 , L 2 and L 3 are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 11 to R 14 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer from 1 to 20;
  • y is an integer from 0 to 20;
  • w and z are each independently an integer from 1 to 20;
  • L 1 'and L' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 21 to R 23 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • b, c and d are each independently an integer from 0 to 20;
  • a is an integer of 0-2.
  • R 1 to R 3 of the silicon compound of Formula 6, Formula 7 or Formula 8 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms.
  • L 1 , L 2 and L 3 are each independently alkylene having 1 to 7 carbon atoms or cycloalkylene having 5 to 7 carbon atoms
  • R 11 to R 14 are each independently hydrogen or alkyl having 1 to 7 carbon atoms
  • n is an integer from 1 to 5
  • y is an integer from 0 to 5
  • w and z may be each independently an integer of 1 to 5.
  • Silicon nitride film etching composition may include 60 to 95% by weight of phosphoric acid and 0.01 to 3% by weight of the silicon compound based on the total weight of the silicon nitride film etching composition.
  • the silicon nitride film etching composition according to an embodiment of the present invention, may be 200 or more.
  • the silicon nitride film etching composition according to an embodiment of the present invention may further include at least one selected from a surfactant, a metal ion sequestrant, an antioxidant, and a corrosion inhibitor.
  • the present invention also provides a method of selectively etching a silicon nitride film compared to a silicon oxide film using the silicon nitride film etching composition, and a method of manufacturing a semiconductor device including the etching method.
  • the silicon nitride film etching composition of the present invention can suppress the etching of the silicon oxide film, can etch the silicon nitride film with high selectivity, minimize the damage of the silicon oxide film, and effectively prevent the generation of particles, thereby preventing unwanted damage in the etching process Since it is possible to prevent the problem of deteriorating the produced device characteristics.
  • the silicon nitride film etching composition of the present invention at least one ethylene oxide (EO) repeating unit is bonded, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon such as alkyl, cycloalkyl or alkenyl. Since the group includes a stable silicon compound having a bonded structure, the phosphoric acid heated to a high temperature does not etch the silicon oxide layer due to the stability of the silicon compound in the etching process, and prevents side reactions of the silicon compound to prevent etching of the particles.
  • the silicon nitride film can be selectively etched without generation.
  • the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
  • the silicon nitride film etching composition of the present invention is excellent in storage stability, and can maintain a stable etching rate and high etching selectivity to the silicon nitride film even after repeated etching processes.
  • etch selectivity (E SiNx / E SiO2 ) refers to the ratio of the etching rate (E SiNx ) of the silicon nitride film to the etching rate (E SiO2 ) of the silicon oxide film.
  • etch selectivity E SiNx / E SiO2 )
  • the term “change in etching selectivity” refers to an absolute value for a difference in etching selectivity to an initial etching selectivity when the etching process is repeatedly performed two or more times using the same etching composition.
  • etch rate drift refers to the rate of change of the etching rate relative to the initial etching rate when the etching process is repeatedly performed two or more times using the same etching composition.
  • the etching ability that is, the etching rate tends to decrease and is defined as a reduction rate, and the change rate is of course interpreted as the same meaning.
  • halogen herein means a fluorine, chlorine, bromine or iodine atom.
  • alkyl refers to a straight or pulverized saturated hydrocarbon monovalent group consisting solely of carbon and hydrogen atoms, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, Octyl, nonyl, and the like.
  • alkoxy refers to a monovalent group in which oxygen and alkyl are bonded, where "alkyl” is as defined above. Examples of such alkoxy include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
  • alkenyl refers to a straight chain or branched unsaturated hydrocarbon monovalent group containing one or more double bonds between two or more carbon atoms, specifically, ethenyl, propenyl, prop-1- En-2yl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3 -Dimethyl-2-butenyl and the like.
  • cycloalkyl refers to a saturated carbocyclic monovalent group consisting of one or more rings, specifically including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Do not.
  • alkylene refers to a straight or pulverized saturated hydrocarbon divalent group consisting solely of carbon and hydrogen atoms, specifically methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, Pentylene, hexylene, octylene, nonylene, and the like.
  • cycloalkylene refers to a saturated carbocyclic divalent group consisting of one or more rings, specifically including cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, etc. It is not limited to this.
  • the present invention is phosphoric acid; And a silicon-based compound represented by Chemical Formula 1; and a silicon nitride film etching composition including the silicon-based compound, wherein the silicon-based compound is a component capable of suppressing etching of silicon oxide.
  • R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or ego;
  • L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
  • L 3 is cycloalkylene having 3 to 8 carbon atoms
  • Q is -O- or -N [(CH 2 CH 2 O) y -R 12 ]-;
  • A is -O- or -N [(CH 2 CH 2 O) z -R 13 ]-;
  • R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer of 0 to 5
  • L may be the same or different from each other
  • A may be the same or different from each other
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • y and z are each independently an integer from 0 to 20;
  • L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • a ' is -O- or -N [(CH 2 CH 2 O) d -R 23 ]-;
  • R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • a is an integer of 0 to 5
  • L ' may be the same or different from each other
  • A' may be the same or different from each other
  • b, c and d are each independently an integer of 0 to 20.
  • the silicon compound of Formula 1 has a structure in which at least one ethylene oxide repeating unit is bonded to a terminal nitrogen atom, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon group such as alkyl, cycloalkyl, or alkenyl is bonded. It is characterized by the structure.
  • the silicon-based compound of Chemical Formula 1 has excellent solubility in water due to increased hydrogen bonding with water due to ethylene oxide repeating units, and high temperature etching process due to hydrocarbon groups bonded to terminal oxygen atoms of the ethylene oxide repeating units. Side reactions of the sub-system compounds are prevented.
  • the phosphoric acid heated to a high temperature during the etching process prevents the silicon oxide film from being etched and prevents side reactions from occurring, thereby preventing particles from being generated, thereby allowing the silicon nitride film to be selectively etched without defects of the substrate. do.
  • Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (2) and formula (3) in terms of preventing the etching of the silicon oxide film.
  • R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or ego;
  • L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
  • L 3 is cycloalkylene having 3 to 8 carbon atoms
  • R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer of 0 to 5
  • L may be the same or different from each other
  • A may be the same or different from each other
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • y and z are each independently an integer from 0 to 20;
  • L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • a is an integer of 0 to 5
  • L ' may be the same or different from each other
  • A' may be the same or different from each other
  • b, c and d are each independently an integer of 0 to 20.
  • the silicon-based compound of Formula 2 exhibits excellent solubility due to the ethylene oxide group bonded to the terminal in the molecule, and prevents side reactions of the silicon-based compound during the high temperature etching process due to the hydrocarbon group bonded to the terminal oxygen atom of the ethylene oxide repeating unit Since it is prevented from occurring, stability in a high temperature etching process is maintained and the silicon oxide etching rate can be effectively reduced to effectively improve the silicon nitride / oxide selection ratio.
  • the silicon-based compound of Formula 3 exhibits excellent solubility due to the ethylene oxide repeating unit bonded to the nitrogen atom in the molecule, and side reaction of the silicon-based compound during the high temperature etching process due to the hydrocarbon group bonded to the terminal oxygen atom of the ethylene oxide repeating unit. By preventing the occurrence of particles, it is possible to maintain the stability in the high temperature etching process and effectively reduce the silicon oxide etch rate to effectively improve the silicon nitride / oxide selectivity ratio.
  • Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (4) or (5) in terms of preventing the etching of the silicon oxide film.
  • R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or ego;
  • L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
  • L 3 is cycloalkylene having 3 to 8 carbon atoms
  • R 11 is hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 10 carbon atoms;
  • n is an integer from 1 to 20;
  • x is an integer from 1 to 10;
  • L 1 ′ and L 2 ′ are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 31 and R 32 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • b is an integer of 0-20.
  • Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (6), formula (7) or formula (8) in terms of preventing the etching of the silicon oxide film.
  • R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or ego;
  • L 1 , L 2 and L 3 are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 11 to R 14 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • n is an integer from 1 to 20;
  • y is an integer from 0 to 20;
  • w and z are each independently an integer from 1 to 20;
  • L 1 'and L' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
  • R 21 to R 23 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
  • b, c and d are each independently an integer from 0 to 20;
  • a is an integer of 0-2.
  • Silicon-based compound according to an embodiment of the present invention is preferably in the general formula (4) or (5) wherein R 1 to R 3 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 and L 2 are each independently alkylene having 1 to 7 carbon atoms, cycloalkylene having 5 to 7 carbon atoms, or — (CH 2 ) x —L 3 —; L 3 is cycloalkylene having 5 to 7 carbon atoms; R 11 is hydrogen or alkyl of 1 to 7 carbon atoms; n is an integer from 1 to 10; x may be at least one selected from a silicon-based compound which is an integer of 2 to 7.
  • R 1 to R 3 in Formula 4 or Formula 5 are each independently halogen, hydroxy or alkoxy having 1 to 4 carbon atoms;
  • L 1 and L 2 are each independently alkylene having 2 to 5 carbon atoms, cycloalkylene having 5 to 6 carbon atoms, or — (CH 2 ) c —L 3 —;
  • L 3 is cycloalkylene having 5 to 7 carbon atoms;
  • R 11 is hydrogen or alkyl of 1 to 4 carbon atoms;
  • n is an integer from 1 to 10;
  • x may be at least one selected from a silicon-based compound which is an integer of 2 to 5.
  • Silicon-based compound according to an embodiment of the present invention is even more preferably R 1 to R 3 in Formula 4 or Formula 5 are each independently chloro, hydroxy, methoxy, ethoxy or butoxy; L 1 and L 2 are each independently ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene, cyclohexylene or Is; R 11 is hydrogen, methyl, ethyl, propyl or butyl; n may be at least one selected from silicon-based compounds having an integer of 1 to 10.
  • Silicon-based compound according to an embodiment of the present invention is preferably R 1 to R 3 in Formula 6, 7 or 8 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 , L 2 and L 3 are each independently alkylene having 1 to 7 carbon atoms or cycloalkylene having 5 to 7 carbon atoms; R 11 to R 14 are each independently hydrogen or alkyl having 1 to 7 carbon atoms; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
  • R 1 to R 3 in Formula 6, 7 or 8 are each independently halogen, hydroxy or alkoxy having 1 to 4 carbon atoms;
  • L 1 , L 2 and L 3 are each independently alkylene having 2 to 5 carbon atoms or cycloalkylene having 5 to 6 carbon atoms;
  • R 11 to R 14 are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
  • n is an integer from 1 to 5;
  • y is an integer from 0 to 5;
  • w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
  • R 1 to R 3 in Formula 6, 7 or 8 are each independently chloro, hydroxy, methoxy, ethoxy or butoxy.
  • L 1 , L 2 and L 3 are each independently ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene or cyclohexylene
  • R 11 to R 14 are each independently hydrogen, methyl, ethyl, propyl or butyl
  • n is an integer from 1 to 5
  • y is an integer from 0 to 5
  • w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
  • the silicon-based compound according to an embodiment of the present invention may be at least one silicon-based compound specifically selected from the following structures, but is not limited thereto.
  • Phosphoric acid included in the silicon nitride film etching composition provides hydrogen ions in the composition, and serves to etch the silicon nitride film by maintaining high temperature process conditions.
  • the silicon nitride film etching composition of the present invention may contain a residual amount of water, and the water is not particularly limited, and is preferably deionized water, and more preferably has a resistivity of 18 Pa ⁇ cm or more as deionized water for a semiconductor process. It is good.
  • the content of phosphoric acid, silicon-based compound and water constituting the silicon nitride film etching composition according to an embodiment of the present invention is not particularly limited, but is 60 to 95% by weight of phosphoric acid based on the total weight of the silicon nitride film etching composition, and 0.01-0.05% silicon-based compound. It is preferred to include from 3% by weight and the balance of water. Within the above range, high silicon oxide / nitride selectivity and improved silicon nitride etching rate can be realized while maintaining high temperature stability during the semiconductor etching process, and particle formation can be effectively suppressed.
  • the silicon nitride film etching composition of the present invention when the phosphoric acid content is less than 60% by weight, the silicon nitride film etching rate is lowered, so that the nitride film may not be easily removed, and when the phosphoric acid content is more than 95% by weight, silicon oxide film etching The speed can be increased to reduce the silicon nitride / oxide selectivity.
  • the silicon nitride film etching composition according to an embodiment of the present invention may include 70 to 90% by weight of phosphoric acid, 0.05 to 1% by weight of silicon-based compound and the balance of water based on the total weight of the silicon nitride film etching composition.
  • stability in a high temperature etching process is maintained and the silicon oxide etching rate can be effectively reduced to effectively improve the silicon nitride / oxide selection ratio and prevent the generation of particles.
  • the etching rate of the silicon oxide layer and the silicon nitride layer may be kept constant.
  • the silicon nitride film etching composition according to an embodiment of the present invention may include 75 to 85% by weight of phosphoric acid, 0.05 to 0.5% by weight of silicon-based compound and the balance of water based on the total weight of the silicon nitride film etching composition.
  • the stability of the etching process at a high temperature of 140 ° C. or more is maintained to completely suppress the generation of particles and to significantly reduce the silicon oxide etching rate, thereby realizing a very high silicon nitride / oxide selection ratio, and repeatedly etching. After the process, stable etching rate and high etching selectivity to the silicon nitride film can be maintained.
  • the silicon nitride film etching composition according to an embodiment of the present invention may further include at least one additive selected from inorganic acids, organic acids and ammonium salts as needed to help stabilize the etching by-products, and is known in the art. If there is one, you can use it without limitation.
  • the content of the additive is not particularly limited, but may be further included as 0.01 to 10% by weight based on the total weight of the silicon nitride film etching composition.
  • the inorganic acid may be at least one selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide, perchloric acid, and boric acid;
  • the organic acid is formic acid, acetic acid, diacetic acid, imino diacetic acid, methanesulfonic acid, ethanesulfonic acid, lactic acid, ascorbic acid, oxalic acid, propionic acid, butanoic acid, valeric acid, butylacetic acid, enantiic acid, capric acid, tartaric acid, succinic acid, malic acid , Maleic acid, malonic acid, glycolic acid, gluconic acid, glycoic acid, glutaric acid, adipic acid, D-glucanic acid, itaconic acid, citraconic acid, mesaconic acid, 2-oxoglutaric acid, trimellitic acid, At least one selected from the group consisting of endortal,
  • the silicon nitride film etching composition according to an embodiment of the present invention may further include any additives commonly used in the art to improve etching performance, and the optional additives include surfactants, antioxidants, Corrosion inhibitors and the like can be used.
  • the surfactant is used to remove the etched residue, and can be used without limitation as long as it is dissolved in the silicon nitride film etching composition of the present invention, for example, anionic surfactants, cationic surfactants or nonionic surfactants Can be used.
  • anionic surfactants include amines such as C 8 H 17 NH 2
  • examples of the anionic surfactant include hydrocarbon based carboxylic acids such as C 8 H 17 COOH and hydrocarbon based such as C 8 H 17 SO 3 H.
  • a sulfonic acid H (CF 2) there may be mentioned fluorine-containing carboxylic acids such as 6 COOH, a non-ionic surfactant may be mentioned ethers such as polyoxyalkylene alkyl ether.
  • the surfactant may be further included in an amount of 0.0005 to 5% by weight based on the total weight of the silicon nitride film etching composition.
  • the antioxidants and corrosion inhibitors are used to prevent corrosion of metals or metal compounds used as semiconductor device materials in an etching process.
  • the antioxidants and corrosion inhibitors may be used without limitation as long as they are used in the industry.
  • One or more types selected from compounds consisting of azole compounds, amine compounds, acid compounds and polyhydric alcohol compounds can be used.
  • azole compounds examples include 5-aminotetrazole, 5-methyl-1H-tetrazole, 1H-tetrazole-5-acetic acid, imidazole, 2-methylimidazole, and 1- (3-aminopropyl) -imidazole.
  • amine compounds examples include p-phenylenediamine, polyaniline, aniline, N-phenyl-p-phenylenediamine, tyramine, triamine hydrochloride, hexamethylenetetramine, urea, dibutylamine, piperazine, 1- (2- Hydroxyethyl) piperazine, 2-methylpiperazine, triethylamine, 2-dimethylaminoethanol and the like can be exemplified.
  • the acid compounds include glycine, nicotinic acid, sodium gluconate, valine, glutamic acid, aspartic acid, ascorbic acid, nitrobenzene, picric acid, and the like. D-sorbitol etc. can be illustrated as said polyhydric alcohol compound.
  • the antioxidant and corrosion inhibitor may be further included in an amount of 0.01 to 10% by weight based on the total weight of the silicon nitride film etching composition.
  • the etching rate of the silicon nitride film of the silicon nitride film etching composition is 50 to 80 ⁇ / min
  • the etching rate of the silicon oxide film is 0 to 0.4 dl / min
  • the silicon nitride film / oxide etching selectivity (E SiNx / E SiO2 ) may be 200 or more, preferably ⁇ .
  • the silicon nitride film / oxide film selectivity may be ⁇ .
  • the silicon nitride film etching composition of the present invention when the silicon nitride film and the silicon oxide film are mixed, the silicon nitride film is selectively rapidly etched with little etching effect on the silicon oxide film, thus increasing the silicon nitride film / oxide film selection ratio in the semiconductor process. Can be implemented.
  • the silicon nitride film etching composition of the present invention implements high temperature stability due to the silicon-based compound to prevent the phosphoric acid heated to a high temperature to etch the silicon oxide film to prevent side reactions to prevent side reactions to prevent substrate defects
  • the silicon nitride film etching rate may be maintained, and excellent semiconductor device characteristics may be realized.
  • the silicon nitride film etching composition of the present invention effectively inhibits particle generation and can selectively etch the silicon nitride film with excellent stability even during high temperature semiconductor etching process, and stable etching rate and etching selectivity to the silicon nitride film even after repeated etching processes. Can be given.
  • the present invention provides a method for selectively etching the silicon nitride film compared to the silicon oxide film using the etching composition.
  • the etching method may be performed according to a method commonly used in the art.
  • the silicon nitride film by etching the silicon nitride film faster than the silicon oxide film, the silicon nitride film can be selectively etched, and do not form particles during the etching process more stable silicon The nitride film can be etched.
  • the silicon oxide film can be effectively prevented from being removed or damaged unnecessarily.
  • the silicon nitride film is a concept including a SiN, SiON, doped SiN film, etc., and means a film quality that is frequently used as an insulating film when forming a gate electrode.
  • the silicon oxide film is not limited as long as it is a silicon oxide film commonly used in the art, for example, SOD (Spin On Dielectric) film, HDP (High Density Plasma) film, thermal oxide (BpG) (Borophosphate Silicate Glass) ), PSG (Phospho Silicate Glass), BSG (Boro Silicate Glass), PSZ (Polysilazane), FSG (Fluorinated Silicate Glass), LPTEOS (Low Pressure Tetra Ethyl Ortho Silicate), PETEOS (Plasma Enhanced Tetra Ethyl) Ortho Silicate (HTO), High Temperature Oxide (HTO), Medium Temperature Oxide (MTO), Undopped Silicate (USG), Spin On Glass (SOG), Advanced Planarization Layer (ALP), Atomic Layer Deposition ) Film, PE-Plasma Enhanced oxide, O3-TEOS (O3-Tetra Ethyl Ortho Silicate) film and at least one selected from the group consisting of a silicon oxide
  • the silicon oxide film or silicon nitride film may be formed in various thicknesses according to the purpose.
  • the silicon oxide film or the silicon nitride film may be independently formed to a thickness of 100 to 3,000 ⁇ , but is not limited thereto.
  • the process of selectively etching the nitride film using the silicon nitride film etching composition of the present invention may be performed according to a method known in the art, and examples thereof include a method of dipping, spraying, and the like.
  • the process temperature may be 100 ° C. or more, preferably in the range of 100 to 500 ° C., more preferably in the range of 100 to 300 ° C., and the appropriate temperature may be changed as necessary in consideration of other processes and other factors. Can be.
  • the present invention provides a method of manufacturing a semiconductor device including an etching process performed using the silicon nitride film etching composition.
  • the kind of said semiconductor element is not specifically limited in this invention.
  • the etching process is characterized in that the silicon nitride film is selectively etched with respect to the silicon oxide film without causing particle problems.
  • the silicon nitride film and the silicon oxide film are alternately stacked or mixed, selective etching of the silicon nitride film is possible, and by effectively suppressing the damage of the silicon oxide film, the etching is performed. Minimize damage to the silicon oxide film by In addition, it is possible to completely prevent the generation of particles that were a problem in the conventional etching process to ensure the stability and reliability of the process.
  • the etching method according to the present invention can selectively remove the silicon nitride film compared to the silicon oxide film and effectively prevent particle generation, and at the same time maintain the etching rate and the etching selectivity in constant despite several times of etching process. Particle generation can be completely prevented and can be efficiently applied to various processes requiring selective etching of the silicon nitride film with respect to the silicon oxide film.
  • Silicon-based compounds Si-2 to Si-9 and silicon-based compounds Si-12 to Si-19 were prepared in a similar manner to Preparation Example 1 or Preparation Example 2, and the prepared silicon-based compounds Si-2 to Si-9 and The structures of Si-12 to Si-19 are as follows.
  • the silicon nitride film (SiN film) wafer and the silicon oxide film (thermal oxide film) were deposited in the same manner as in the semiconductor manufacturing process using the CVD method.
  • LP-TEOS (Low Pressure Tetra Ethyl Ortho Silicate) films were prepared, respectively.
  • the thickness before etching was measured using an ellipsometer (M-2000U, J.A WOOLLAM, Inc.) which is a thin film thickness measuring instrument.
  • the etching process was performed by dipping the wafer into the silicon nitride film etching solution (Examples 1 to 20 and Comparative Examples 1 to 6) maintained at an etching temperature of 157 ° C. in a quartz bath for 10 minutes. After the etching was completed, the resultant was washed with ultrapure water, and the remaining etchant and moisture were completely dried using a drying apparatus.
  • the etching rate was calculated by dividing the difference between the thickness before etching and the thickness after etching using an ellipsometer (J.A WOOLLAM, M-2000U) by etching time (minutes), and the results are shown in Table 2 below.
  • the etching selectivity (the etching rate of the silicon nitride film / the etching rate of the silicon oxide film) was calculated according to the ratio of the etching rate of the silicon nitride film and the etching rate of the silicon oxide film, and is shown in Table 2 below.
  • the surface of the silicon oxide film etched in Examples 1 to 20 and Comparative Examples 1 to 6 was measured by an electron scanning microscope (SEM) to examine whether particles were generated, and are described in Table 2 below.
  • the silicon nitride film etching compositions of Examples 1 to 20 exhibited excellent etching rates with respect to the silicon nitride films and low etching rates regardless of the types of silicon oxide films, resulting in excellent etching selectivity. In addition, particle generation was effectively prevented.
  • the silicon nitride film etching compositions of Comparative Examples 1 and 2 had a significant drop in silicon oxide etch inhibition, resulting in a low etching selectivity, and particles were not suitable for selectively and stably etching the silicon nitride film.
  • the silicon nitride film etching composition of Comparative Example 3 did not generate particles during the etching process, the etching selectivity with respect to the silicon nitride film was very low, and thus was not suitable for selectively etching the silicon nitride film.
  • the silicon oxide film etching rate was significantly reduced compared to the silicon nitride film etching compositions of Comparative Examples 1 to 3 that do not include the silicon-based compound. Therefore, when the silicon-based compound of Formula 1 is included in the silicon nitride film etching composition, it was found that the etching selectivity of the silicon nitride film to the silicon oxide film is significantly increased by significantly suppressing the etching of the silicon oxide film.
  • the silicon nitride film etching compositions of Examples 1 to 10 at least one ethylene oxide repeating unit is bonded at a terminal thereof, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit or a hydrocarbon group such as alkyl is bonded.
  • the silicon nitride film etching composition of Examples 11 to 20 at least one ethylene oxide repeating unit is bonded to a terminal nitrogen atom, hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon group such as alkyl is used.
  • Including the bonded silicon-based compound effectively prevented the generation of particles generated during the etching process compared to Comparative Examples 4 to 6 containing APTES, HPST and THSPS, respectively.
  • the silicon-based compound of Formula 1 included in the silicon nitride film etching composition of the present invention is very stable under high temperature acid conditions, the phosphoric acid heated to high temperature during the etching process effectively inhibits etching of the silicon oxide film.
  • the phosphoric acid heated to high temperature during the etching process effectively inhibits etching of the silicon oxide film.
  • the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
  • the silicon nitride film etching composition of the present invention can suppress the etching of the silicon oxide film, can etch the silicon nitride film with high selectivity, minimize the damage of the silicon oxide film, and effectively prevent the generation of particles, thereby preventing unwanted damage in the etching process Since it is possible to prevent the problem of deteriorating the produced device characteristics.
  • the silicon nitride film etching composition of the present invention at least one ethylene oxide (EO) repeating unit is bonded, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon such as alkyl, cycloalkyl or alkenyl. Since the group includes a stable silicon compound having a bonded structure, the phosphoric acid heated to a high temperature does not etch the silicon oxide layer due to the stability of the silicon compound in the etching process, and prevents side reactions of the silicon compound to prevent etching of the particles.
  • the silicon nitride film can be selectively etched without generation.
  • the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
  • the silicon nitride film etching composition of the present invention is excellent in storage stability, and can maintain a stable etching rate and high etching selectivity to the silicon nitride film even after repeated etching processes.

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Abstract

The present invention relates to a silicon nitride film etching composition, which can minimize the etching rate to a silicon oxide film, can selectively etch a silicon nitride film, leaves no particles on a substrate, and is stable at a high temperature.

Description

실리콘 질화막 식각 조성물Silicon Nitride Etch Composition
본 발명은 실리콘 산화막에 대한 식각율을 최소화하고, 실리콘 질화막을 선택적으로 식각할 수 있으며, 기판에 파티클이 잔존하지 않으며, 고온에서 안정한 실리콘 질화막 식각 조성물에 관한 것이다.The present invention relates to a silicon nitride film etching composition which minimizes an etching rate for a silicon oxide film, selectively etches a silicon nitride film, particles do not remain on a substrate, and is stable at high temperatures.
실리콘 산화막(SiO2) 및 실리콘 질화막(SiNx)은 반도체 제조공정에서 사용되는 대표적인 절연막으로 사용되며, 각각 단독으로 사용되거나 혹은 1층 이상의 실리콘 산화막 및 1층 이상의 실리콘 질화막이 교대로 적층되어 사용되기도 한다. 또한 상기 실리콘 산화막 및 실리콘 질화막은 금속 배선과 같은 도전성 패턴을 형성하기 위한 하드마스크(Hard mask)로서도 사용된다.Silicon oxide film (SiO2) and silicon nitride film (SiNx) are used as representative insulating films used in semiconductor manufacturing processes, and may be used alone, or one or more layers of silicon oxide and one or more layers of silicon nitride are alternately stacked. In addition, the silicon oxide film and the silicon nitride film are also used as a hard mask for forming a conductive pattern such as a metal wiring.
종래 실리콘 질화막의 습식 식각 공정은 일반적으로 160℃ 내외의 고온에서 인산과 탈이온수의 혼합물을 이용하고 있으나, 고온의 식각 공정에서 인산으로 인한 실리콘 산화막의 식각을 방지하기 위한 목적으로 규소계 첨가제들을 첨가한 식각 조성물이 제안되었다.Conventionally, the wet etching process of the silicon nitride film generally uses a mixture of phosphoric acid and deionized water at a high temperature of about 160 ° C., but adds silicon-based additives for the purpose of preventing etching of the silicon oxide film due to phosphoric acid in the high temperature etching process. One etching composition has been proposed.
그러나, 인산과 규산이나 규산염을 포함하는 식각 조성물을 이용하여 질화막을 식각하는 경우 규산이나 규산염은 기판에 영향을 미칠 수 있는 파티클을 유발하여 오히려 반도체 제조공정에 적합하지 못한 문제점이 있다.However, when the nitride film is etched using an etching composition including phosphoric acid, silicic acid, or silicate, silicic acid or silicate may cause particles that may affect the substrate, and thus may not be suitable for a semiconductor manufacturing process.
한국공개특허 제2011-0037741호 및 제2011-0037766호에는 인산에 옥심실란 및 알콕시실란 화합물을 넣어서 실리콘 산화막의 식각 속도를 1 Å/min 이하로 제어하였고, 여기에 불소 화합물을 넣어 질화막 식각 속도를 높였다고 개시하고 있다. 그러나, 통상의 실란 화합물은 물과 접촉 시 고분자의 실록산 화합물(Si-O-Si)이 형성되어 웨이퍼 표면에 이물이 붙는 문제가 있고, 실리콘 화합물의 손실로 인한 실리콘 질화막 및 산화막의 식각 속도를 균일하게 유지할 수 없는 문제가 발생한다. In Korean Patent Laid-Open Nos. 2011-0037741 and 2011-0037766, an oxime silane and an alkoxysilane compound were added to phosphoric acid to control the etching rate of the silicon oxide film to 1 Å / min or less, and a fluorine compound was added to the nitride film etch rate. It is starting to raise. However, the conventional silane compound has a problem in that a polymer siloxane compound (Si-O-Si) is formed upon contact with water and foreign matters adhere to the wafer surface, and the etching rate of the silicon nitride film and the oxide film due to the loss of the silicon compound is uniform. Problems arise.
이상 살펴본 바와 같이, 종래 식각 조성물에 포함되는 실리콘 첨가제들의 안정성 문제로 인하여 파티클이 유발하여 반도체 제조공정에 많은 문제들을 야기시키고 있다. As described above, particles are induced due to stability problems of the silicon additives included in the conventional etching composition, causing many problems in the semiconductor manufacturing process.
따라서, 첨가제 안정성이 보장되며, 실리콘 산화막에 데미지를 주지 않으면서 실리콘 질화막을 선택적으로 식각할 수 있는 실리콘 질화막에 대한 고선택비 식각액이 요구되고 있는 상황이다.Therefore, the additive stability is guaranteed, a high selectivity etchant for the silicon nitride film that can selectively etch the silicon nitride film without damaging the silicon oxide film is required.
본 발명은 실리콘 산화막의 식각을 최소화하면서 실리콘 질화막을 선택적으로 식각할 수 있으며, 반도체 소자 특성에 영향을 미치는 파티클 발생 등의 문제점을 갖지 않는 고선택비의 실리콘 질화막 식각 조성물을 제공하는데 목적이 있다.The present invention can selectively etch a silicon nitride film while minimizing the etching of the silicon oxide film, and an object of the present invention is to provide a high selectivity silicon nitride film etching composition that does not have problems such as generation of particles affecting semiconductor device characteristics.
본 발명은 인산; 및 하기 화학식 1로 표시되는 규소계 화합물;을 포함하는 실리콘 질화막 식각 조성물을 제공한다.The present invention is phosphoric acid; And a silicon-based compound represented by Formula 1 below.
[화학식 1][Formula 1]
Figure PCTKR2018003652-appb-I000001
Figure PCTKR2018003652-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐 또는
Figure PCTKR2018003652-appb-I000002
이고;R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or
Figure PCTKR2018003652-appb-I000002
ego;
L 및 L1은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
Q는 -O- 또는 -N[(CH2CH2O)y-R12]-이며;Q is -O- or -N [(CH 2 CH 2 O) y -R 12 ]-;
A는 -O- 또는 -N[(CH2CH2O)z-R13]-이고;A is -O- or -N [(CH 2 CH 2 O) z -R 13 ]-;
R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
Q'는 -O- 또는 -N[(CH2CH2O)c-R22]-이며;Q 'is -O- or -N [(CH 2 CH 2 O) c -R 22 ]-;
A'는 -O- 또는 -N[(CH2CH2O)d-R23]-이고;A 'is -O- or -N [(CH 2 CH 2 O) d -R 23 ]-;
R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 상기 규소계 화합물은 하기 화학식 2 또는 화학식 3으로 표시되는 규소계 화합물일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, the silicon-based compound may be a silicon-based compound represented by the following formula (2) or (3).
[화학식 2][Formula 2]
Figure PCTKR2018003652-appb-I000003
Figure PCTKR2018003652-appb-I000003
[화학식 3][Formula 3]
Figure PCTKR2018003652-appb-I000004
Figure PCTKR2018003652-appb-I000004
상기 화학식 2 및 3에서,In Chemical Formulas 2 and 3,
R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐,
Figure PCTKR2018003652-appb-I000005
또는
Figure PCTKR2018003652-appb-I000006
이고;R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms,
Figure PCTKR2018003652-appb-I000005
or
Figure PCTKR2018003652-appb-I000006
ego;
L 및 L1은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 상기 규소계 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 규소계 화합물일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, the silicon-based compound may be a silicon-based compound represented by the following formula (4) or (5).
[화학식 4][Formula 4]
Figure PCTKR2018003652-appb-I000007
Figure PCTKR2018003652-appb-I000007
[화학식 5][Formula 5]
Figure PCTKR2018003652-appb-I000008
Figure PCTKR2018003652-appb-I000008
상기 화학식 4 및 5에서,In Chemical Formulas 4 and 5,
R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시,
Figure PCTKR2018003652-appb-I000009
또는
Figure PCTKR2018003652-appb-I000010
이고; R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms,
Figure PCTKR2018003652-appb-I000009
or
Figure PCTKR2018003652-appb-I000010
ego;
L1 및 L2는 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is a cycloalkylene having 3 to 8 carbon atoms;
R11은 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 is hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 10 carbon atoms;
n은 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
L1' 및 L2'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 ′ and L 2 ′ are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R31 및 R32은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 31 and R 32 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
b는 0 내지 20의 정수이다.b is an integer of 0-20.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 상기 화학식 4 또는 5의 규소계 화합물의 상기 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1 및 L2는 각각 독립적으로 탄소수 1 내지 7의 알킬렌, 탄소수 5 내지 7의 사이클로알킬렌 또는 -(CH2)x-L3- 이며; L3는 탄소수 5 내지 7의 사이클로알킬렌이며; R11은 수소 또는 탄소수 1 내지 7의 알킬이고; n은 1 내지 10의 정수이고; x는 2 내지 7의 정수일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, each of R 1 to R 3 of the silicon compound of Formula 4 or 5 is independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 and L 2 are each independently alkylene having 1 to 7 carbon atoms, cycloalkylene having 5 to 7 carbon atoms, or — (CH 2 ) x —L 3 —; L 3 is cycloalkylene having 5 to 7 carbon atoms; R 11 is hydrogen or alkyl of 1 to 7 carbon atoms; n is an integer from 1 to 10; x can be an integer from 2 to 7.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 상기 규소계 화합물은 하기 화학식 6, 화학식 7 또는 화학식 8로 표시되는 규소계 화합물일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, the silicon-based compound may be a silicon-based compound represented by the following formula (6), (7) or (8).
[화학식 6][Formula 6]
Figure PCTKR2018003652-appb-I000011
Figure PCTKR2018003652-appb-I000011
[화학식 7][Formula 7]
Figure PCTKR2018003652-appb-I000012
Figure PCTKR2018003652-appb-I000012
[화학식 8][Formula 8]
Figure PCTKR2018003652-appb-I000013
Figure PCTKR2018003652-appb-I000013
상기 화학식 6 내지 8에서,In Chemical Formulas 6 to 8,
R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시 또는
Figure PCTKR2018003652-appb-I000014
이고;R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or
Figure PCTKR2018003652-appb-I000014
ego;
L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 , L 2 and L 3 are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R11 내지 R14는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 14 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
y는 0 내지 20의 정수이고;y is an integer from 0 to 20;
w 및 z는 각각 독립적으로 1 내지 20의 정수이고;w and z are each independently an integer from 1 to 20;
L1' 및 L'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 'and L' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R21 내지 R23은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이고;b, c and d are each independently an integer from 0 to 20;
a은 0 내지 2의 정수이다.a is an integer of 0-2.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 상기 화학식 6, 화학식 7 또는 화학식 8의 규소계 화합물의 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 7의 알킬렌 또는 탄소수 5 내지 7의 사이클로알킬렌이며; R11 내지 R14는 각각 독립적으로 수소 또는 탄소수 1 내지 7의 알킬이고; n는 1 내지 5의 정수이고; y는 0 내지 5의 정수이고; w 및 z는 각각 독립적으로 1 내지 5의 정수일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, R 1 to R 3 of the silicon compound of Formula 6, Formula 7 or Formula 8 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms. ; L 1 , L 2 and L 3 are each independently alkylene having 1 to 7 carbon atoms or cycloalkylene having 5 to 7 carbon atoms; R 11 to R 14 are each independently hydrogen or alkyl having 1 to 7 carbon atoms; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z may be each independently an integer of 1 to 5.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물은 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 인산 60 내지 95 중량% 및 규소계 화합물 0.01 내지 3 중량%을 포함할 수 있다.Silicon nitride film etching composition according to an embodiment of the present invention may include 60 to 95% by weight of phosphoric acid and 0.01 to 3% by weight of the silicon compound based on the total weight of the silicon nitride film etching composition.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 있어서, 실리콘 질화막/산화막 식각 선택비는 200 이상일 수 있다.In the silicon nitride film etching composition according to an embodiment of the present invention, the silicon nitride film / oxide etching selectivity may be 200 or more.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물은 계면활성제, 금속 이온 봉쇄제, 산화방지제 및 부식방지제로부터 선택되는 적어도 하나를 더 포함할 수 있다.The silicon nitride film etching composition according to an embodiment of the present invention may further include at least one selected from a surfactant, a metal ion sequestrant, an antioxidant, and a corrosion inhibitor.
또한, 본 발명은 상기 실리콘 질화막 식각 조성물을 이용하여 실리콘 산화막 대비 실리콘 질화막을 선택적으로 식각하는 방법 및 상기 식각 방법을 포함하는 반도체 소자의 제조 방법을 제공한다.The present invention also provides a method of selectively etching a silicon nitride film compared to a silicon oxide film using the silicon nitride film etching composition, and a method of manufacturing a semiconductor device including the etching method.
본 발명의 실리콘 질화막 식각 조성물은 실리콘 산화막의 식각을 억제하고, 실리콘 질화막을 높은 선택성으로 식각할 수 있고, 실리콘 산화막의 데미지를 최소화하고, 파티클 발생을 효과적으로 방지하여, 식각 공정에서 원치 않는 손상을 방지할 수 있기 때문에 제조된 소자 특성이 저하되는 문제를 방지할 수 있다. The silicon nitride film etching composition of the present invention can suppress the etching of the silicon oxide film, can etch the silicon nitride film with high selectivity, minimize the damage of the silicon oxide film, and effectively prevent the generation of particles, thereby preventing unwanted damage in the etching process Since it is possible to prevent the problem of deteriorating the produced device characteristics.
또한 본 발명의 실리콘 질화막 식각 조성물은 에틸렌옥사이드(Ethylene oxide, EO) 반복 단위가 적어도 하나 결합되고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 수소가 결합되거나, 알킬, 사이클로알킬 또는 알케닐과 같은 탄화수소 기가 결합된 구조의 안정적인 규소계 화합물을 포함하고 있으므로, 식각 공정에서 상기 규소계 화합물의 안정성으로 인하여 고온으로 가열된 인산이 상기 실리콘 산화막을 식각하지 못하도록 하면서, 상기 규소계 화합물의 부반응을 막아 파티클의 발생 없이 실리콘 질화막을 선택적으로 식각할 수 있도록 한다. 따라서, 본 발명에 따른 실리콘 질화막 식각 조성물은 질화막 식각 시 산화막의 막질 손상이나 산화막의 식각으로 인한 전기적 특성 저하 및 파티클 발생을 방지하면서 질화막을 선택적으로 식각함으로써, 소자 특성을 향상시킬 수 있다.In the silicon nitride film etching composition of the present invention, at least one ethylene oxide (EO) repeating unit is bonded, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon such as alkyl, cycloalkyl or alkenyl. Since the group includes a stable silicon compound having a bonded structure, the phosphoric acid heated to a high temperature does not etch the silicon oxide layer due to the stability of the silicon compound in the etching process, and prevents side reactions of the silicon compound to prevent etching of the particles. The silicon nitride film can be selectively etched without generation. Therefore, the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
또한, 본 발명의 실리콘 질화막 식각 조성물은 보관 안정성이 우수하고, 반복적인 식각 공정 후에도 실리콘 질화막에 대한 안정적인 식각속도 및 높은 식각 선택성을 유지할 수 있다.In addition, the silicon nitride film etching composition of the present invention is excellent in storage stability, and can maintain a stable etching rate and high etching selectivity to the silicon nitride film even after repeated etching processes.
이하, 본 발명에 대하여 보다 구체적으로 설명한다. 이 때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely. Unless otherwise defined in the technical terms and scientific terms used at this time, have a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs, unnecessarily obscure the subject matter of the present invention in the following description Description of known functions and configurations that may be omitted.
본 명세서 내 용어, "식각 선택비(ESiNx / ESiO2)"는 실리콘 산화막의 식각 속도(ESiO2) 대비 실리콘 질화막의 식각 속도(ESiNx)의 비를 의미한다. 또한, 실리콘 산화막의 식각 속도가 거의 0에 가까워지거나 식각 선택비의 수치가 큰 경우, 실리콘 질화막을 선택적으로 식각할 수 있음을 의미한다.As used herein, the term "etch selectivity (E SiNx / E SiO2 )" refers to the ratio of the etching rate (E SiNx ) of the silicon nitride film to the etching rate (E SiO2 ) of the silicon oxide film. In addition, when the etching rate of the silicon oxide film approaches zero or the value of the etching selectivity is large, it means that the silicon nitride film can be selectively etched.
본 명세서 내 용어, "식각 선택비의 변화"은 동일한 식각 조성물을 이용하여 2회 이상 식각 공정을 반복 수행하는 경우, 초기 식각 선택비 대비 식각 선택비의 차이에 대한 절대값을 의미한다.As used herein, the term “change in etching selectivity” refers to an absolute value for a difference in etching selectivity to an initial etching selectivity when the etching process is repeatedly performed two or more times using the same etching composition.
본 명세서 내 용어, "식각 속도 감소율(Etch rate drift, △ERD)"는 동일한 식각 조성물을 이용하여 2회 이상 식각 공정을 반복 수행하는 경우, 초기 식각 속도 대비 식각 속도의 변화율을 의미한다. 구체적으로, 식각 속도 감소율 △ERD는 △ERD(%) = [1 - {(n 회 이상 사용 시 식각속도) / (1 회 사용 시 식각속도)}]×100 로 계산되며, n은 2 이상의 자연수이다. 일반적으로 식각 공정을 반복 수행함에 따라 식각능, 즉 식각 속도가 감소되는 경향을 보임에 따라 감소율이라 정의하며, 변화율 역시 동일한 의미로 해석됨은 물론이다.As used herein, the term “etch rate drift (ΔERD)” refers to the rate of change of the etching rate relative to the initial etching rate when the etching process is repeatedly performed two or more times using the same etching composition. Specifically, the etching rate reduction rate ΔERD is calculated as ΔERD (%) = [1-{(etching speed when used more than n times) / (etching speed when used once)} × 100, and n is a natural number of 2 or more. to be. In general, as the etching process is repeatedly performed, the etching ability, that is, the etching rate tends to decrease and is defined as a reduction rate, and the change rate is of course interpreted as the same meaning.
본 명세서 내 용어 "할로겐"은 불소, 염소, 브롬 또는 요오드 원자를 의미한다. The term "halogen" herein means a fluorine, chlorine, bromine or iodine atom.
본 명세서 내 용어 "알킬"은 탄소 및 수소 원자만으로 구성된 직쇄 또는 분쇄 포화 탄화수소 1가 기를 의미하는 것으로, 구체적으로 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, t-부틸, 펜틸, 헥실, 옥틸, 노닐 등을 포함하지만 이에 한정되지는 않는다.As used herein, the term "alkyl" refers to a straight or pulverized saturated hydrocarbon monovalent group consisting solely of carbon and hydrogen atoms, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, Octyl, nonyl, and the like.
본 명세서 내 용어 "알콕시"는 산소와 알킬이 결합된 1가 기를 의미하는 것으로, 여기서 ‘알킬’은 상기 정의한 바와 같다. 이러한 알콕시의 예로는 메톡시, 에톡시, 이소프로폭시, 부톡시, 이소부톡시, t-부톡시 등을 포함하지만 이에 한정되지는 않는다.As used herein, the term "alkoxy" refers to a monovalent group in which oxygen and alkyl are bonded, where "alkyl" is as defined above. Examples of such alkoxy include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
본 명세서 내 용어 "알케닐"은 두 개 이상의 탄소 원자들 사이에 하나 이상의 이중 결합을 포함하는 직쇄 또는 분쇄의 불포화 탄화수소 1가 기를 의미하는 것으로, 구체적으로 에테닐, 프로펜일, 프로프-1-엔-2일, 1-부테닐, 2-부테닐, 이소부틸레닐, 1-펜테닐, 2-펜테닐, 3-메틸-1-부테닐, 2-메틸-2-부테닐, 2,3-디메틸-2-부테닐 등을 포함하지만 이에 한정되지는 않는다.As used herein, the term "alkenyl" refers to a straight chain or branched unsaturated hydrocarbon monovalent group containing one or more double bonds between two or more carbon atoms, specifically, ethenyl, propenyl, prop-1- En-2yl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3 -Dimethyl-2-butenyl and the like.
본 명세서 내 용어 "사이클로알킬"은 하나 이상의 고리로 구성된 포화 카보사이클릭 1가 기를 의미하는 것으로, 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 사이클로헥실, 사이클로헵틸 등을 포함하지만, 이에 한정되지는 않는다.As used herein, the term "cycloalkyl" refers to a saturated carbocyclic monovalent group consisting of one or more rings, specifically including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Do not.
본 명세서 내 용어 "알킬렌"은 탄소 및 수소 원자만으로 구성된 직쇄 또는 분쇄 포화 탄화수소 2가 기를 의미하는 것으로, 구체적으로 메틸렌, 에틸렌, 프로필렌, 이소프로필렌, 부틸렌, 이소부틸렌, t-부틸렌, 펜틸렌, 헥실렌, 옥틸렌, 노닐렌 등을 포함하지만 이에 한정되지는 않는다. As used herein, the term "alkylene" refers to a straight or pulverized saturated hydrocarbon divalent group consisting solely of carbon and hydrogen atoms, specifically methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, Pentylene, hexylene, octylene, nonylene, and the like.
본 명세서 내 용어 "사이클로알킬렌"은 하나 이상의 고리로 구성된 포화 카보사이클릭 2가 기를 의미하는 것으로, 구체적으로 사이클로프로필렌, 사이클로부틸렌, 사이클로펜틸렌, 사이클로헥실렌, 사이클로헵틸렌 등을 포함하지만, 이에 한정되지는 않는다.As used herein, the term "cycloalkylene" refers to a saturated carbocyclic divalent group consisting of one or more rings, specifically including cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, etc. It is not limited to this.
본 발명은 인산; 및 하기 화학식 1로 표시되는 규소계 화합물;을 포함하는 실리콘 질화막 식각 조성물에 관한 것으로, 상기 규소계 화합물은 실리콘 산화물의 식각을 억제할 수 있는 성분이다.The present invention is phosphoric acid; And a silicon-based compound represented by Chemical Formula 1; and a silicon nitride film etching composition including the silicon-based compound, wherein the silicon-based compound is a component capable of suppressing etching of silicon oxide.
[화학식 1][Formula 1]
Figure PCTKR2018003652-appb-I000015
Figure PCTKR2018003652-appb-I000015
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐 또는
Figure PCTKR2018003652-appb-I000016
이고;R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or
Figure PCTKR2018003652-appb-I000016
ego;
L 및 L1은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
Q는 -O- 또는 -N[(CH2CH2O)y-R12]-이며;Q is -O- or -N [(CH 2 CH 2 O) y -R 12 ]-;
A는 -O- 또는 -N[(CH2CH2O)z-R13]-이고;A is -O- or -N [(CH 2 CH 2 O) z -R 13 ]-;
R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
Q'는 -O- 또는 -N[(CH2CH2O)c-R22]-이며;Q 'is -O- or -N [(CH 2 CH 2 O) c -R 22 ]-;
A'는 -O- 또는 -N[(CH2CH2O)d-R23]-이고;A 'is -O- or -N [(CH 2 CH 2 O) d -R 23 ]-;
R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
상기 화학식 1의 규소계 화합물은 말단 질소 원자에 에틸렌옥사이드 반복단위가 적어도 하나 결합된 구조 및 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 수소가 결합되거나, 알킬, 사이클로알킬 또는 알케닐과 같은 탄화수소 기가 결합된 구조를 특징으로 한다. 상기 화학식 1의 규소계 화합물은 에틸렌 옥사이드 반복단위로 인하여 물과의 수소결합이 증가하여 물에 대한 용해도가 우수하고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 결합된 탄화수소 기로 인하여 고온 식각 공정시 규소계 화합물의 부반응이 방지된다. 이러한 규소계 화합물의 안정성으로 인하여 식각 공정시 고온으로 가열된 인산이 실리콘 산화막을 식각하는 것을 억제함과 동시에 부반응의 발생을 막아 파티클 발생을 방지함으로서 기판의 불량 없이 실리콘 질화막이 선택적으로 식각될 수 있게 한다.The silicon compound of Formula 1 has a structure in which at least one ethylene oxide repeating unit is bonded to a terminal nitrogen atom, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon group such as alkyl, cycloalkyl, or alkenyl is bonded. It is characterized by the structure. The silicon-based compound of Chemical Formula 1 has excellent solubility in water due to increased hydrogen bonding with water due to ethylene oxide repeating units, and high temperature etching process due to hydrocarbon groups bonded to terminal oxygen atoms of the ethylene oxide repeating units. Side reactions of the sub-system compounds are prevented. Due to the stability of the silicon-based compound, the phosphoric acid heated to a high temperature during the etching process prevents the silicon oxide film from being etched and prevents side reactions from occurring, thereby preventing particles from being generated, thereby allowing the silicon nitride film to be selectively etched without defects of the substrate. do.
본 발명의 일 실시예에 따른 규소계 화합물은 실리콘 산화막의 식각 방지 측면에서 바람직하게는 상기 화학식 2 및 화학식 3으로 표시되는 규소계 화합물 중 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (2) and formula (3) in terms of preventing the etching of the silicon oxide film.
[화학식 2][Formula 2]
Figure PCTKR2018003652-appb-I000017
Figure PCTKR2018003652-appb-I000017
[화학식 3][Formula 3]
Figure PCTKR2018003652-appb-I000018
Figure PCTKR2018003652-appb-I000018
상기 화학식 2 및 3에서,In Chemical Formulas 2 and 3,
R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐,
Figure PCTKR2018003652-appb-I000019
또는
Figure PCTKR2018003652-appb-I000020
이고;R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms,
Figure PCTKR2018003652-appb-I000019
or
Figure PCTKR2018003652-appb-I000020
ego;
L1 및 L2은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
상기 화학식 2의 규소계 화합물은 분자 내 말단에 결합된 에틸렌옥사이드 기로 인해 우수한 용해도를 나타내고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 결합된 탄화수소 기로 인하여 고온 식각 공정시 규소계 화합물의 부반응을 막아 파티클 발생을 방지하므로, 고온의 식각 공정에서의 안정성이 유지되며 실리콘 산화막 식각 속도를 효과적으로 감소시켜 실리콘 질화막/산화막 선택비를 효과적으로 개선할 수 있다.The silicon-based compound of Formula 2 exhibits excellent solubility due to the ethylene oxide group bonded to the terminal in the molecule, and prevents side reactions of the silicon-based compound during the high temperature etching process due to the hydrocarbon group bonded to the terminal oxygen atom of the ethylene oxide repeating unit Since it is prevented from occurring, stability in a high temperature etching process is maintained and the silicon oxide etching rate can be effectively reduced to effectively improve the silicon nitride / oxide selection ratio.
상기 화학식 3의 규소계 화합물은 분자 내 질소 원자에 결합된 에틸렌 옥사이드 반복단위로 인해 우수한 용해도를 나타내고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 결합된 탄화수소 기로 인하여 고온 식각 공정시 규소계 화합물의 부반응을 막아 파티클 발생을 방지하므로, 고온의 식각 공정에서의 안정성이 유지되며 실리콘 산화막 식각 속도를 효과적으로 감소시켜 실리콘 질화막/산화막 선택비를 효과적으로 개선할 수 있다.The silicon-based compound of Formula 3 exhibits excellent solubility due to the ethylene oxide repeating unit bonded to the nitrogen atom in the molecule, and side reaction of the silicon-based compound during the high temperature etching process due to the hydrocarbon group bonded to the terminal oxygen atom of the ethylene oxide repeating unit. By preventing the occurrence of particles, it is possible to maintain the stability in the high temperature etching process and effectively reduce the silicon oxide etch rate to effectively improve the silicon nitride / oxide selectivity ratio.
본 발명의 일 실시예에 따른 규소계 화합물은 실리콘 산화막의 식각 방지 측면에서 바람직하게는 상기 화학식 4 또는 화학식 5로 표시되는 규소계 화합물 중 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (4) or (5) in terms of preventing the etching of the silicon oxide film.
[화학식 4][Formula 4]
Figure PCTKR2018003652-appb-I000021
Figure PCTKR2018003652-appb-I000021
[화학식 5][Formula 5]
Figure PCTKR2018003652-appb-I000022
Figure PCTKR2018003652-appb-I000022
상기 화학식 4 및 5에서,In Chemical Formulas 4 and 5,
R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시,
Figure PCTKR2018003652-appb-I000023
또는
Figure PCTKR2018003652-appb-I000024
이고; R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms,
Figure PCTKR2018003652-appb-I000023
or
Figure PCTKR2018003652-appb-I000024
ego;
L1 및 L2는 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
R11은 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 is hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 10 carbon atoms;
n은 1 내지 20의 정수이고;n is an integer from 1 to 20;
x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
L1' 및 L2'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 ′ and L 2 ′ are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R31 및 R32은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 31 and R 32 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
b는 0 내지 20의 정수이다.b is an integer of 0-20.
본 발명의 일 실시예에 따른 규소계 화합물은 실리콘 산화막의 식각 방지 측면에서 바람직하게는 상기 화학식 6, 화학식 7 또는 화학식 8로 표시되는 규소계 화합물 중 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention may be at least one selected from the silicon-based compound represented by the formula (6), formula (7) or formula (8) in terms of preventing the etching of the silicon oxide film.
[화학식 6][Formula 6]
Figure PCTKR2018003652-appb-I000025
Figure PCTKR2018003652-appb-I000025
[화학식 7][Formula 7]
Figure PCTKR2018003652-appb-I000026
Figure PCTKR2018003652-appb-I000026
[화학식 8][Formula 8]
Figure PCTKR2018003652-appb-I000027
Figure PCTKR2018003652-appb-I000027
상기 화학식 6 내지 8에서,In Chemical Formulas 6 to 8,
R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시 또는
Figure PCTKR2018003652-appb-I000028
이고;R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or
Figure PCTKR2018003652-appb-I000028
ego;
L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 , L 2 and L 3 are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R11 내지 R14는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 14 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
y는 0 내지 20의 정수이고;y is an integer from 0 to 20;
w 및 z는 각각 독립적으로 1 내지 20의 정수이고;w and z are each independently an integer from 1 to 20;
L1' 및 L'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 'and L' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
R21 내지 R23은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
b, c 및 d는 각각 독립적으로 0 내지 20의 정수이고;b, c and d are each independently an integer from 0 to 20;
a은 0 내지 2의 정수이다.a is an integer of 0-2.
본 발명의 일 실시예에 따른 규소계 화합물은 바람직하게는 상기 화학식 4 또는 화학식 5에서 상기 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1 및 L2는 각각 독립적으로 탄소수 1 내지 7의 알킬렌, 탄소수 5 내지 7의 사이클로알킬렌 또는 -(CH2)x-L3- 이며; L3는 탄소수 5 내지 7의 사이클로알킬렌이며; R11은 수소 또는 탄소수 1 내지 7의 알킬이고; n은 1 내지 10의 정수이고; x는 2 내지 7의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention is preferably in the general formula (4) or (5) wherein R 1 to R 3 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 and L 2 are each independently alkylene having 1 to 7 carbon atoms, cycloalkylene having 5 to 7 carbon atoms, or — (CH 2 ) x —L 3 —; L 3 is cycloalkylene having 5 to 7 carbon atoms; R 11 is hydrogen or alkyl of 1 to 7 carbon atoms; n is an integer from 1 to 10; x may be at least one selected from a silicon-based compound which is an integer of 2 to 7.
본 발명의 일 실시예에 따른 규소계 화합물은 더 바람직하게는 상기 화학식 4 또는 화학식 5에서 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 4의 알콕시이고; L1 및 L2는 각각 독립적으로 탄소수 2 내지 5의 알킬렌, 탄소수 5 내지 6의 사이클로알킬렌 또는 -(CH2)c-L3- 이며; L3는 탄소수 5 내지 7의 사이클로알킬렌이며; R11은 수소 또는 탄소수 1 내지 4의 알킬이고; n은 1 내지 10의 정수이고; x는 2 내지 5의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.More preferably, the silicon-based compound according to an embodiment of the present invention, R 1 to R 3 in Formula 4 or Formula 5 are each independently halogen, hydroxy or alkoxy having 1 to 4 carbon atoms; L 1 and L 2 are each independently alkylene having 2 to 5 carbon atoms, cycloalkylene having 5 to 6 carbon atoms, or — (CH 2 ) c —L 3 —; L 3 is cycloalkylene having 5 to 7 carbon atoms; R 11 is hydrogen or alkyl of 1 to 4 carbon atoms; n is an integer from 1 to 10; x may be at least one selected from a silicon-based compound which is an integer of 2 to 5.
본 발명의 일 실시예에 따른 규소계 화합물은 더욱 더 바람직하게는 상기 화학식 4 또는 화학식 5에서 R1 내지 R3가 각각 독립적으로 클로로, 히드록시, 메톡시, 에톡시 또는 부톡시이고; L1 및 L2가 각각 독립적으로 에틸렌, 프로필렌, 부틸렌, 펜틸렌, 헥실렌, 사이클로펜틸렌, 사이클로헥실렌 또는
Figure PCTKR2018003652-appb-I000029
이며; R11은 수소, 메틸, 에틸, 프로필 또는 부틸이고; n이 1 내지 10의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention is even more preferably R 1 to R 3 in Formula 4 or Formula 5 are each independently chloro, hydroxy, methoxy, ethoxy or butoxy; L 1 and L 2 are each independently ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene, cyclohexylene or
Figure PCTKR2018003652-appb-I000029
Is; R 11 is hydrogen, methyl, ethyl, propyl or butyl; n may be at least one selected from silicon-based compounds having an integer of 1 to 10.
본 발명의 일 실시예에 따른 규소계 화합물은 바람직하게는 상기 화학식 6, 화학식 7 또는 화학식 8에서 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 7의 알킬렌 또는 탄소수 5 내지 7의 사이클로알킬렌이며; R11 내지 R14는 각각 독립적으로 수소 또는 탄소수 1 내지 7의 알킬이고; n는 1 내지 5의 정수이고; y는 0 내지 5의 정수이고; w 및 z는 각각 독립적으로 1 내지 5의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.Silicon-based compound according to an embodiment of the present invention is preferably R 1 to R 3 in Formula 6, 7 or 8 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 , L 2 and L 3 are each independently alkylene having 1 to 7 carbon atoms or cycloalkylene having 5 to 7 carbon atoms; R 11 to R 14 are each independently hydrogen or alkyl having 1 to 7 carbon atoms; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
본 발명의 일 실시예에 따른 규소계 화합물은 더 바람직하게는 상기 화학식 6, 화학식 7 또는 화학식 8에서 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 4의 알콕시이고; L1, L2 및 L3은 각각 독립적으로 탄소수 2 내지 5의 알킬렌 또는 탄소수 5 내지 6의 사이클로알킬렌이며; R11 내지 R14는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬이고; n는 1 내지 5의 정수이고; y는 0 내지 5의 정수이고; w 및 z는 각각 독립적으로 1 내지 5의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.More preferably, the silicon-based compound according to an embodiment of the present invention, R 1 to R 3 in Formula 6, 7 or 8 are each independently halogen, hydroxy or alkoxy having 1 to 4 carbon atoms; L 1 , L 2 and L 3 are each independently alkylene having 2 to 5 carbon atoms or cycloalkylene having 5 to 6 carbon atoms; R 11 to R 14 are each independently hydrogen or alkyl having 1 to 4 carbon atoms; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
본 발명의 일 실시예에 따른 규소계 화합물은 더욱 더 바람직하게는 상기 화학식 6, 화학식 7 또는 화학식 8에서 R1 내지 R3는 각각 독립적으로 클로로, 히드록시, 메톡시, 에톡시 또는 부톡시이고; L1, L2 및 L3은 각각 독립적으로 에틸렌, 프로필렌, 부틸렌, 펜틸렌, 헥실렌, 사이클로펜틸렌 또는 사이클로헥실렌이며; R11 내지 R14는 각각 독립적으로 수소, 메틸, 에틸, 프로필 또는 부틸이고; n는 1 내지 5의 정수이고; y는 0 내지 5의 정수이고; w 및 z는 각각 독립적으로 1 내지 5의 정수인 규소계 화합물 중에서 선택되는 적어도 하나일 수 있다.The silicon-based compound according to an embodiment of the present invention is even more preferably R 1 to R 3 in Formula 6, 7 or 8 are each independently chloro, hydroxy, methoxy, ethoxy or butoxy. ; L 1 , L 2 and L 3 are each independently ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene or cyclohexylene; R 11 to R 14 are each independently hydrogen, methyl, ethyl, propyl or butyl; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z may each independently be at least one selected from a silicon-based compound which is an integer of 1 to 5.
본 발명의 일 실시예에 따른 규소계 화합물은 구체적으로 하기 구조로부터 선택되는 적어도 하나의 규소계 화합물일 수 있으나, 이에 한정되지는 않는다.The silicon-based compound according to an embodiment of the present invention may be at least one silicon-based compound specifically selected from the following structures, but is not limited thereto.
Figure PCTKR2018003652-appb-I000030
Figure PCTKR2018003652-appb-I000030
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물에 포함되는 인산은 조성물 내에 수소 이온을 제공하며, 고온의 공정 조건을 유지할 수 있게 하여 실리콘 질화막을 식각하는 역할을 한다.Phosphoric acid included in the silicon nitride film etching composition according to an embodiment of the present invention provides hydrogen ions in the composition, and serves to etch the silicon nitride film by maintaining high temperature process conditions.
본 발명의 실리콘 질화막 식각 조성물은 물을 잔량 포함할 수 있으며, 상기 물은 특별히 한정되는 것은 아니며, 탈이온수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온수로서 비저항값이 18㏁ㆍcm 이상인 것이 좋다.The silicon nitride film etching composition of the present invention may contain a residual amount of water, and the water is not particularly limited, and is preferably deionized water, and more preferably has a resistivity of 18 Pa · cm or more as deionized water for a semiconductor process. It is good.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물을 구성하는 인산, 규소계 화합물 및 물의 함량은 특별히 제한되지는 않으나, 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 인산 60 내지 95 중량%, 규소계 화합물 0.01 내지 3 중량% 및 잔량의 물을 포함하는 것이 바람직하다. 상기 범위 내에서 반도체 식각 공정시 고온안정성을 유지하면서도 높은 실리콘 산화막/질화막 선택비 및 향상된 실리콘 질화막 식각 속도를 구현할 수 있으며 파티클의 형성을 효과적으로 억제할 수 있다.The content of phosphoric acid, silicon-based compound and water constituting the silicon nitride film etching composition according to an embodiment of the present invention is not particularly limited, but is 60 to 95% by weight of phosphoric acid based on the total weight of the silicon nitride film etching composition, and 0.01-0.05% silicon-based compound. It is preferred to include from 3% by weight and the balance of water. Within the above range, high silicon oxide / nitride selectivity and improved silicon nitride etching rate can be realized while maintaining high temperature stability during the semiconductor etching process, and particle formation can be effectively suppressed.
본 발명의 실리콘 질화막 식각 조성물에서 상기 인산의 함량이 60 중량% 미만인 경우 실리콘 질화막 식각 속도가 저하되어 질화막이 용이하게 제거되지 않을 수 있고, 상기 인산의 함량이 95 중량%를 초과하는 경우 실리콘 산화막 식각 속도가 증가하여 실리콘 질화막/산화막 선택비가 감소될 수 있다. In the silicon nitride film etching composition of the present invention, when the phosphoric acid content is less than 60% by weight, the silicon nitride film etching rate is lowered, so that the nitride film may not be easily removed, and when the phosphoric acid content is more than 95% by weight, silicon oxide film etching The speed can be increased to reduce the silicon nitride / oxide selectivity.
보다 좋게는, 본 발명의 일 예에 따른 실리콘 질화막 식각 조성물은 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 인산 70 내지 90 중량%, 규소계 화합물 0.05 내지 1 중량% 및 잔량의 물을 포함할 수 있다. 이와 같은 범위에서 고온의 식각 공정에서의 안정성이 유지되며 실리콘 산화막 식각 속도를 효과적으로 감소시켜 실리콘 질화막/산화막 선택비를 효과적으로 개선할 수 있고 파티클의 발생을 방지할 수 있다. 더불어 반복적인 식각 공정을 수행함에도 불구하고 실리콘 산화막 및 실리콘 질화막에 대한 식각 속도를 일정하게 유지시킬 수 있다.More preferably, the silicon nitride film etching composition according to an embodiment of the present invention may include 70 to 90% by weight of phosphoric acid, 0.05 to 1% by weight of silicon-based compound and the balance of water based on the total weight of the silicon nitride film etching composition. In such a range, stability in a high temperature etching process is maintained and the silicon oxide etching rate can be effectively reduced to effectively improve the silicon nitride / oxide selection ratio and prevent the generation of particles. In addition, despite the repetitive etching process, the etching rate of the silicon oxide layer and the silicon nitride layer may be kept constant.
특히 바람직하게, 본 발명의 일 예에 따른 실리콘 질화막 식각 조성물은 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 인산 75 내지 85 중량%, 규소계 화합물 0.05 내지 0.5 중량% 및 잔량의 물을 포함할 수 있다. 이와 같은 범위에서 140 ℃ 이상의 고온의 식각 공정에서의 안정성이 유지되어 파티클의 발생을 완벽하게 억제하며 실리콘 산화막 식각 속도를 현저하게 감소시켜 매우 높은 실리콘 질화막/산화막 선택비를 구현할 수 있고, 반복적인 식각 공정 후에도 실리콘 질화막에 대한 안정적인 식각속도 및 높은 식각 선택성을 유지할 수 있다.Particularly preferably, the silicon nitride film etching composition according to an embodiment of the present invention may include 75 to 85% by weight of phosphoric acid, 0.05 to 0.5% by weight of silicon-based compound and the balance of water based on the total weight of the silicon nitride film etching composition. In this range, the stability of the etching process at a high temperature of 140 ° C. or more is maintained to completely suppress the generation of particles and to significantly reduce the silicon oxide etching rate, thereby realizing a very high silicon nitride / oxide selection ratio, and repeatedly etching. After the process, stable etching rate and high etching selectivity to the silicon nitride film can be maintained.
또한, 본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물은 식각 부산물을 안정화하는데 도움을 주기 위하여 필요에 따라 무기산, 유기산 및 암모늄염으로부터 선택되는 적어도 하나의 첨가제를 더 포함할 수 있으며, 당업계에 알려져 있는 것이라면 제한 없이 사용할 수 있다. 상기 첨가제의 함량은 특별히 제한되지는 않으나, 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 0.01 내지 10 중량%로 더 포함될 수 있다.In addition, the silicon nitride film etching composition according to an embodiment of the present invention may further include at least one additive selected from inorganic acids, organic acids and ammonium salts as needed to help stabilize the etching by-products, and is known in the art. If there is one, you can use it without limitation. The content of the additive is not particularly limited, but may be further included as 0.01 to 10% by weight based on the total weight of the silicon nitride film etching composition.
구체적인 일례로 상기 무기산은 불화수소산, 염산, 황산, 질산, 과산화수소산, 과염소산 및 붕산으로 이루어진 군으로부터 선택되는 적어도 하나일 수 있고; 상기 유기산은 포름산, 아세트산, 디아세트산, 이미노디아세트산, 메탄술폰산, 에탄술폰산, 락트산, 아스코빅산, 옥살산, 프로피온산, 부탄산, 발레르산, 부틸아세트산, 에난틱산, 카프르산, 타르타르산, 숙신산, 말산, 말레산, 말론산, 글리콜산, 글루콘산, 글리코산, 글루타르산, 아디프산, D-글루칸산, 이타콘산, 시트라콘산, 메사콘산, 2-옥소글루타르산, 트리멜리트산, 엔도탈, 글루탐산, 메틸숙신산 및 시트르산으로 이루어진 군으로부터 선택되는 적어도 하나일 수 있고; 상기 암모늄염은 (NH4)2SO4, (NH4)3PO4, NH4NO3, NH4CH3CO2, NH4HCO3, NH4Cl, NH4F, NH4HF2 및 NH4BF4로 이루어진 군으로부터 선택되는 적어도 하나일 수 있다.As a specific example, the inorganic acid may be at least one selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide, perchloric acid, and boric acid; The organic acid is formic acid, acetic acid, diacetic acid, imino diacetic acid, methanesulfonic acid, ethanesulfonic acid, lactic acid, ascorbic acid, oxalic acid, propionic acid, butanoic acid, valeric acid, butylacetic acid, enantiic acid, capric acid, tartaric acid, succinic acid, malic acid , Maleic acid, malonic acid, glycolic acid, gluconic acid, glycoic acid, glutaric acid, adipic acid, D-glucanic acid, itaconic acid, citraconic acid, mesaconic acid, 2-oxoglutaric acid, trimellitic acid, At least one selected from the group consisting of endortal, glutamic acid, methylsuccinic acid and citric acid; The ammonium salt is (NH 4 ) 2 SO 4 , (NH 4 ) 3 PO 4 , NH 4 NO 3 , NH 4 CH 3 CO 2 , NH 4 HCO 3 , NH 4 Cl, NH 4 F, NH 4 HF 2 and NH At least one selected from the group consisting of 4 BF 4 .
또한, 본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물은 식각 성능을 향상시키기 위하여 당업계에서 통상적으로 사용되는 임의의 첨가제를 더 포함할 수 있으며, 상기 임의의 첨가제로는 계면활성제, 산화방지제, 부식방지제 등을 사용할 수 있다.In addition, the silicon nitride film etching composition according to an embodiment of the present invention may further include any additives commonly used in the art to improve etching performance, and the optional additives include surfactants, antioxidants, Corrosion inhibitors and the like can be used.
상기 계면활성제는 식각된 잔사를 제거하기 위하여 사용되는 것으로, 본 발명의 실리콘 질화막 식각 조성물에 용해되는 것이면 제한없이 사용할 수 있으며, 일예로 음이온성 계면활성제, 양이온성 계면활성제 또는 비이온성 계면활성제를 모두 사용할 수 있다. 상기 양이온성 계면활성제로는 C8H17NH2 등의 아민류를 들 수 있고, 상기 음이온성 계면활성제로는 C8H17COOH 등의 탄화수소계 카르복시산, C8H17SO3H 등의 탄화수소계 술폰산, H(CF2)6COOH 등의 불소계 카르복실산을 들 수 있고, 비이온성 계면활성제로는 폴리옥시알킬렌알킬에테르 등의 에테르류를 들 수 있다. 상기 계면활성제는 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 0.0005 내지 5중량%로 더 포함될 수 있다.The surfactant is used to remove the etched residue, and can be used without limitation as long as it is dissolved in the silicon nitride film etching composition of the present invention, for example, anionic surfactants, cationic surfactants or nonionic surfactants Can be used. Examples of the cationic surfactant include amines such as C 8 H 17 NH 2 , and examples of the anionic surfactant include hydrocarbon based carboxylic acids such as C 8 H 17 COOH and hydrocarbon based such as C 8 H 17 SO 3 H. a sulfonic acid, H (CF 2) there may be mentioned fluorine-containing carboxylic acids such as 6 COOH, a non-ionic surfactant may be mentioned ethers such as polyoxyalkylene alkyl ether. The surfactant may be further included in an amount of 0.0005 to 5% by weight based on the total weight of the silicon nitride film etching composition.
상기 산화방지제 및 부식방지제는 식각 공정시 반도체 소자 재료로 사용되는 금속 또는 금속화합물의 부식을 방지하고자 사용되는 것으로, 상기 산화방지제 및 부식방지제로는 업계에서 사용되는 것이면 제한없이 사용 가능하고, 일례로 아졸류 화합물, 아민류 화합물, 산류 화합물 및 다가 알코올류 화합물로 이루어진 화합물로부터 선택된 1종 이상을 사용할 수 있다.The antioxidants and corrosion inhibitors are used to prevent corrosion of metals or metal compounds used as semiconductor device materials in an etching process. The antioxidants and corrosion inhibitors may be used without limitation as long as they are used in the industry. One or more types selected from compounds consisting of azole compounds, amine compounds, acid compounds and polyhydric alcohol compounds can be used.
상기 아졸류 화합물로서는 5-아미노테트라졸, 5-메틸-1H-테트라졸, 1H-테트라졸-5-아세트산, 이미다졸, 2-메틸이미다졸, 1-(3-아미노프로필)-이미다졸, 히스티딘, 4-메틸이미다졸, 1,2,3-트리아졸, 1,2,4-트리아졸, 피라졸, 피리딘, 피리미딘, 피롤, 피롤리돈, 피롤린, 벤조트리아졸, 벤조트리아졸-5-카르복실산, 5-메틸-1H-벤조트리아졸, 인돌, 퓨린, 2-아미노벤즈이미다졸, 아데닌, 구아닌, 톨루트리아졸, 4-메틸-1H-벤조트리아졸, 1H-벤조트리아졸-1-메탄올 등을 예시할 수 있다. 상기 아민류 화합물로서는 p-페닐렌디아민, 폴리아닐린, 아닐린, N-페닐-p-페닐렌디아민, 티라민, 트리아민 히드로클로라이드, 헥사메틸렌테트라민, 우레아, 디부틸아민, 피페라진, 1-(2-히드록시에틸)피페라진, 2-메틸피페라진, 트리에틸아민, 2-디메틸아미노에탄올 등을 예시할 수 있다. 상기 산류 화합물로서는 글리신, 니코틴산, 소듐 글루코네이트, 발린, 글루탐산, 아스파르트산, 아스코르브산, 니트로벤젠, 피크르산 등을 예시할 수 있다. 상기 다가 알코올류 화합물로서는 D-소르비톨 등을 예시할 수 있다. 상기 산화방지제 및 부식방지제는 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 0.01 내지 10 중량%로 더 포함될 수 있다. Examples of the azole compounds include 5-aminotetrazole, 5-methyl-1H-tetrazole, 1H-tetrazole-5-acetic acid, imidazole, 2-methylimidazole, and 1- (3-aminopropyl) -imidazole. , Histidine, 4-methylimidazole, 1,2,3-triazole, 1,2,4-triazole, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidone, pyrroline, benzotriazole, benzo Triazole-5-carboxylic acid, 5-methyl-1H-benzotriazole, indole, purine, 2-aminobenzimidazole, adenine, guanine, tolutriazole, 4-methyl-1H-benzotriazole, 1H -Benzotriazole-1-methanol etc. can be illustrated. Examples of the amine compounds include p-phenylenediamine, polyaniline, aniline, N-phenyl-p-phenylenediamine, tyramine, triamine hydrochloride, hexamethylenetetramine, urea, dibutylamine, piperazine, 1- (2- Hydroxyethyl) piperazine, 2-methylpiperazine, triethylamine, 2-dimethylaminoethanol and the like can be exemplified. Examples of the acid compounds include glycine, nicotinic acid, sodium gluconate, valine, glutamic acid, aspartic acid, ascorbic acid, nitrobenzene, picric acid, and the like. D-sorbitol etc. can be illustrated as said polyhydric alcohol compound. The antioxidant and corrosion inhibitor may be further included in an amount of 0.01 to 10% by weight based on the total weight of the silicon nitride film etching composition.
본 발명의 일 실시예에 따른 실리콘 질화막 식각 조성물을 이용하여 반도체 웨이퍼에서 식각을 수행하는 경우, 상기 실리콘 질화막 식각 조성물의 실리콘 질화막의 식각 속도는 50 내지 80 Å/min이며, 실리콘 산화막의 식각 속도는 0 내지 0.4 Å/min일 수 있고, 실리콘 질화막/산화막 식각 선택비(ESiNx / ESiO2)는 200 이상, 바람직하게는 ∞ 일 수 있다. 특히, 실리콘 산화막에 대한 식각율이 거의 0에 가까우면서 실리콘 질화막을 선택적으로 식각하는 경우 실리콘 질화막/산화막 선택비는 ∞ 일 수 있다. When etching the semiconductor wafer using the silicon nitride film etching composition according to an embodiment of the present invention, the etching rate of the silicon nitride film of the silicon nitride film etching composition is 50 to 80 Å / min, the etching rate of the silicon oxide film is 0 to 0.4 dl / min, the silicon nitride film / oxide etching selectivity (E SiNx / E SiO2 ) may be 200 or more, preferably ∞. Particularly, when the silicon nitride film is selectively etched while the etching rate of the silicon oxide film is almost zero, the silicon nitride film / oxide film selectivity may be ∞.
본 발명의 실리콘 질화막 식각 조성물은 실리콘 질화막과 실리콘 산화막이 혼재하는 경우, 실리콘 산화막에 대하여 식각 영향을 거의 끼치지 않으면서 실리콘 질화막을 선택적으로 빠르게 식각하므로, 반도체 공정에서 높은 실리콘 질화막/산화막 선택비를 구현할 수 있다. In the silicon nitride film etching composition of the present invention, when the silicon nitride film and the silicon oxide film are mixed, the silicon nitride film is selectively rapidly etched with little etching effect on the silicon oxide film, thus increasing the silicon nitride film / oxide film selection ratio in the semiconductor process. Can be implemented.
또한, 본 발명의 실리콘 질화막 식각 조성물은 상기 규소계 화합물로 인해 고온 안정성을 구현하여 고온으로 가열된 인산이 상기 실리콘 산화막을 식각하는 것을 억제함으로서 부반응을 방지하여 이물질이 발생하지 않아 기판 불량을 막을 수 있고, 실리콘 질화막 식각 속도가 유지될 수 있으며, 우수한 반도체 소자 특성을 구현할 수 있다.In addition, the silicon nitride film etching composition of the present invention implements high temperature stability due to the silicon-based compound to prevent the phosphoric acid heated to a high temperature to etch the silicon oxide film to prevent side reactions to prevent side reactions to prevent substrate defects In addition, the silicon nitride film etching rate may be maintained, and excellent semiconductor device characteristics may be realized.
본 발명의 실리콘 질화막 식각 조성물은 파티클 생성을 효과적으로 억제함은 물론 고온의 반도체 식각 공정 중에도 우수한 안정성으로 실리콘 질화막을 선택적으로 식각할 수 있고, 반복적인 식각 공정 후에도 실리콘 질화막에 대한 안정적인 식각속도 및 식각 선택성을 부여할 수 있다.The silicon nitride film etching composition of the present invention effectively inhibits particle generation and can selectively etch the silicon nitride film with excellent stability even during high temperature semiconductor etching process, and stable etching rate and etching selectivity to the silicon nitride film even after repeated etching processes. Can be given.
본 발명은 상기 식각 조성물을 이용하여 실리콘 산화막 대비 실리콘 질화막을 선택적으로 식각하는 방법을 제공한다. 이때, 상기 식각하는 방법은 당업계에서 통상적으로 사용되는 방법에 따라 수행될 수 있다.The present invention provides a method for selectively etching the silicon nitride film compared to the silicon oxide film using the etching composition. In this case, the etching method may be performed according to a method commonly used in the art.
본 발명의 일 실시예에 따른 식각하는 방법에 따르면, 상기 실리콘 질화막을 상기 실리콘 산화막에 비해 보다 빠르게 식각하여, 실리콘 질화막을 선택적으로 식각할 수 있고, 식각 공정 중에 파티클을 형성하지 않아 보다 안정적으로 실리콘 질화막을 식각할 수 있다. 또한 실리콘 산화막이 불필요하게 제거되거나 손상되는 것을 효과적으로 방지할 수 있다.According to the etching method according to an embodiment of the present invention, by etching the silicon nitride film faster than the silicon oxide film, the silicon nitride film can be selectively etched, and do not form particles during the etching process more stable silicon The nitride film can be etched. In addition, the silicon oxide film can be effectively prevented from being removed or damaged unnecessarily.
본 발명에서 실리콘 질화막이라 함은 SiN, SiON, doped SiN 막 등을 포함하는 개념으로서 게이트 전극 등의 형성 시 절연막으로 많이 사용되는 막질을 의미한다.In the present invention, the silicon nitride film is a concept including a SiN, SiON, doped SiN film, etc., and means a film quality that is frequently used as an insulating film when forming a gate electrode.
또한, 상기 실리콘 산화막은 당업계에서 통상적으로 사용되는 실리콘 산화막이라면 제한되지 않으나, 일예로 SOD(Spin On Dielectric)막, HDP(High Density Plasma)막, 열산화막 (thermal oxide), BPSG(Borophosphate Silicate Glass)막, PSG(Phospho Silicate Glass)막, BSG(Boro Silicate Glass)막, PSZ(Polysilazane)막, FSG(Fluorinated Silicate Glass)막, LPTEOS(Low Pressure Tetra Ethyl Ortho Silicate)막, PETEOS(Plasma Enhanced Tetra Ethyl Ortho Silicate)막, HTO(High Temperature Oxide)막, MTO(Medium Temperature Oxide)막, USG(Undopped Silicate Glass)막, SOG(Spin On Glass)막, APL(Advanced Planarization Layer)막, ALD(Atomic Layer Deposition)막, PE-산화막(Plasma Enhanced oxide), O3-TEOS(O3-Tetra Ethyl Ortho Silicate)막 및 그 조합으로 이루어진 군으로부터 선택되는 적어도 하나 이상의 막일 수 있다.In addition, the silicon oxide film is not limited as long as it is a silicon oxide film commonly used in the art, for example, SOD (Spin On Dielectric) film, HDP (High Density Plasma) film, thermal oxide (BpG) (Borophosphate Silicate Glass) ), PSG (Phospho Silicate Glass), BSG (Boro Silicate Glass), PSZ (Polysilazane), FSG (Fluorinated Silicate Glass), LPTEOS (Low Pressure Tetra Ethyl Ortho Silicate), PETEOS (Plasma Enhanced Tetra Ethyl) Ortho Silicate (HTO), High Temperature Oxide (HTO), Medium Temperature Oxide (MTO), Undopped Silicate (USG), Spin On Glass (SOG), Advanced Planarization Layer (ALP), Atomic Layer Deposition ) Film, PE-Plasma Enhanced oxide, O3-TEOS (O3-Tetra Ethyl Ortho Silicate) film and at least one selected from the group consisting of a combination thereof.
이때, 상기 실리콘 산화막 또는 실리콘 질화막은 목적에 따라 다양한 두께로 형성될 수 있다. 예컨대, 상기 실리콘 산화막 또는 실리콘 질화막은 각각 독립적으로 100 내지 3,000Å의 두께로 형성될 수 있나 이에 한정되는 것은 아니다.In this case, the silicon oxide film or silicon nitride film may be formed in various thicknesses according to the purpose. For example, the silicon oxide film or the silicon nitride film may be independently formed to a thickness of 100 to 3,000 Å, but is not limited thereto.
또한, 본 발명의 실리콘 질화막 식각 조성물을 이용하여 질화막을 선택적으로 식각하는 공정은 당업계 주지의 방법에 따라 수행될 수 있으며, 일예로 침지시키는 방법, 분사(spray)하는 방법 등을 들 수 있다. 식각 공정시 공정 온도는 100 ℃ 이상, 바람직하게는 100 내지 500℃의 범위, 보다 바람직하게는 100 내지 300℃의 범위일 수 있으며, 적정 온도는 다른 공정과 기타 요인을 고려하여 필요에 따라 변경될 수 있다.In addition, the process of selectively etching the nitride film using the silicon nitride film etching composition of the present invention may be performed according to a method known in the art, and examples thereof include a method of dipping, spraying, and the like. In the etching process, the process temperature may be 100 ° C. or more, preferably in the range of 100 to 500 ° C., more preferably in the range of 100 to 300 ° C., and the appropriate temperature may be changed as necessary in consideration of other processes and other factors. Can be.
또한, 본 발명은 상기 실리콘 질화막 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조방법을 제공한다.In addition, the present invention provides a method of manufacturing a semiconductor device including an etching process performed using the silicon nitride film etching composition.
상기 반도체 소자의 종류는 본 발명에서 특별히 한정되지 않는다.The kind of said semiconductor element is not specifically limited in this invention.
상기 식각 공정은 파티클 문제를 유발하지 않고, 실리콘 산화막에 대하여 실리콘 질화막을 선택적으로 식각하는 것을 특징으로 한다.The etching process is characterized in that the silicon nitride film is selectively etched with respect to the silicon oxide film without causing particle problems.
본 발명의 일 실시예에 따른 반도체 소자의 제조방법에 따르면, 실리콘 질화막과 실리콘 산화막이 교대로 적층되거나 혼재되어 있는 경우 실리콘 질화막에 대한 선택적 식각이 가능하며, 실리콘 산화막의 손상을 효과적으로 억제함으로써, 식각에 의한 실리콘 산화막의 데미지를 최소화한다. 또한, 종래 식각 공정에서 문제가 되었던 파티클 발생을 완벽히 방지하여 공정의 안정성 및 신뢰성을 확보할 수 있다.According to the method of manufacturing a semiconductor device according to an embodiment of the present invention, when the silicon nitride film and the silicon oxide film are alternately stacked or mixed, selective etching of the silicon nitride film is possible, and by effectively suppressing the damage of the silicon oxide film, the etching is performed. Minimize damage to the silicon oxide film by In addition, it is possible to completely prevent the generation of particles that were a problem in the conventional etching process to ensure the stability and reliability of the process.
따라서, 본 발명에 따른 식각하는 방법은 실리콘 질화막을 실리콘 산화막 대비 선택적으로 제거 가능하고 파티클 발생을 효과적으로 방지할 뿐만 아니라, 식각 공정의 수회 반복에도 불구하고 식각 속도 및 식각 선택비를 일정하게 유지함과 동시에 파티클 발생을 완벽하게 방지할 수 있어, 실리콘 산화막에 대하여 실리콘 질화막의 선택적 식각이 필요한 여러 공정에 효율적으로 적용될 수 있다.Therefore, the etching method according to the present invention can selectively remove the silicon nitride film compared to the silicon oxide film and effectively prevent particle generation, and at the same time maintain the etching rate and the etching selectivity in constant despite several times of etching process. Particle generation can be completely prevented and can be efficiently applied to various processes requiring selective etching of the silicon nitride film with respect to the silicon oxide film.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
[제조예 1] 규소계 화합물 Si-1 [화학식 5에서 R1=R2=R3=에톡시, L1=L2=1,3-프로필렌, n=1, R11=수소에 해당]의 제조Production Example 1 Silicon Compound Si-1 [corresponding to R 1 = R 2 = R 3 = ethoxy, L 1 = L 2 = 1,3-propylene, n = 1, R 11 = hydrogen in Formula 5] Manufacture
Figure PCTKR2018003652-appb-I000031
Figure PCTKR2018003652-appb-I000031
냉각관 및 교반기를 구비한 플라스크에, 트라이에톡시실란 (100 중량부)를 투입하고 2-(3-(알릴옥시)프로폭시)에탄올 (2-(3-(allyloxy)propoxy)ethanol)를 트라이에톡시 실란과 1 : 1의 몰비로 투입하고, 용매로서 에틸아세테이트 (500 중량부)를 투입하였다. 상기 반응 혼합물을 50℃로 가열한 다음, 칼스테트 촉매 (Karstedt’s catalyst) (0.004 중량부)를 투입하고 80℃에서 3시간동안 수소규소화반응(hydrosilylation)시켜 화합물 Si-1을 수득하였다.Into a flask equipped with a cooling tube and a stirrer, triethoxysilane (100 parts by weight) was added and 2- (3- (allyloxy) propoxy) ethanol (2- (3- (allyloxy) propoxy) ethanol) was added thereto. Ethoxy silane was added in a molar ratio of 1: 1, and ethyl acetate (500 parts by weight) was added as a solvent. The reaction mixture was heated to 50 ° C., and then Karlstedt's catalyst (0.004 parts by weight) was added thereto, followed by hydrosilylation at 80 ° C. for 3 hours to obtain compound Si-1.
1H-NMR (500 MHz, CDCl3): δ 0.63(t, 2H), 1.22(t, 9H), 1.5(m, 2H), 1.63(m, 2H), 2.0(Br, 1H), 3.37(m, 6H), 3.56-3.70(m, 4H), 3.83(m, 6H) 1 H-NMR (500 MHz, CDCl 3 ): δ 0.63 (t, 2H), 1.22 (t, 9H), 1.5 (m, 2H), 1.63 (m, 2H), 2.0 (Br, 1H), 3.37 ( m, 6H), 3.56-3.70 (m, 4H), 3.83 (m, 6H)
[제조예 2] 규소계 화합물 Si-11 [화학식 6에서 R1=R2=R3=에톡시, L1=1,3-프로필렌, n=1, y=0, R11=R12=수소에 해당]의 제조Preparation Example 2 Silicon-Based Compound Si-11 In Formula 6, R 1 = R 2 = R 3 = Ethoxy, L 1 = 1,3-propylene, n = 1, y = 0, R 11 = R 12 = Preparation of hydrogen]
Figure PCTKR2018003652-appb-I000032
Figure PCTKR2018003652-appb-I000032
냉각관 및 교반기를 구비한 플라스크에, 트라이에톡시실란 (100 중량부)를 투입하고 2-(알릴아미노)에탄올 (2-(allylamino)ethanol)를 트라이에톡시 실란과 1 : 1의 몰비로 투입하고, 용매로서 에틸아세테이트 (500 중량부)를 투입하였다. 상기 반응 혼합물을 50℃로 가열한 다음, 칼스테트 촉매 (Karstedt’s catalyst) (0.004 중량부)를 투입하고 80℃에서 3시간동안 수소규소화반응(hydrosilylation)시켜 화합물 Si-11을 수득하였다.Into a flask equipped with a cooling tube and a stirrer, triethoxysilane (100 parts by weight) was added and 2- (allylamino) ethanol was added at a molar ratio of triethoxy silane and 1: 1. Ethyl acetate (500 parts by weight) was added as a solvent. The reaction mixture was heated to 50 ° C., and then Karlstedt's catalyst (0.004 parts by weight) was added thereto, followed by hydrosilylation at 80 ° C. for 3 hours to obtain compound Si-11.
1H-NMR (500 MHz, CDCl3): δ 0.67(t, 2H), 1.26(t, 9H), 1.57(m, 2H), 2.2(Br, 2H), 2.55(m, 2H), 2.74(m, 2H), 3.68(m, 2H), 3.84(m, 6H) 1 H-NMR (500 MHz, CDCl 3 ): δ 0.67 (t, 2H), 1.26 (t, 9H), 1.57 (m, 2H), 2.2 (Br, 2H), 2.55 (m, 2H), 2.74 ( m, 2H), 3.68 (m, 2H), 3.84 (m, 6H)
[제조예 3 내지 18] 규소계 화합물 Si-2 내지 Si-9 및 Si-12-19의 제조Preparation Examples 3 to 18 Preparation of Silicon Compounds Si-2 to Si-9 and Si-12-19
상기 제조예 1 또는 제조예 2와 유사한 방법으로 규소계 화합물 Si-2 내지 Si-9 및 규소계 화합물 Si-12 내지 Si-19를 제조하였으며, 제조된 규소계 화합물 Si-2 내지 Si-9 및 Si-12 내지 Si-19의 구조는 다음과 같다.Silicon-based compounds Si-2 to Si-9 and silicon-based compounds Si-12 to Si-19 were prepared in a similar manner to Preparation Example 1 or Preparation Example 2, and the prepared silicon-based compounds Si-2 to Si-9 and The structures of Si-12 to Si-19 are as follows.
Si-2 : (EtO)3Si-CH2CH2CH2-O-CH2CH2CH2-O-(CH2CH2O)2-H [화학식 5에서 R1=R2=R3=에톡시, L1=L2=1,3-프로필렌, n=2, R11=수소에 해당]Si-2: (EtO) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O- (CH 2 CH 2 O) 2 -H [In Formula 5, R 1 = R 2 = R 3 = Ethoxy, L 1 = L 2 = 1,3-propylene, n = 2, R 11 = corresponds to hydrogen]
Si-3 : (HO)3Si-CH2CH2CH2-O-CH2CH2CH2-O-CH2CH2OH [화학식 5에서 R1=R2=R3=히드록시, L1=L2=1,3-프로필렌, n=1, R11=수소에 해당]Si-3: (HO) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CH 2 OH [Formula 5, R 1 = R 2 = R 3 = hydroxy, L 1 = L 2 = 1,3-propylene, n = 1, R 11 = corresponds to hydrogen]
Si-4 : (Cl)3Si-CH2CH2CH2-O-CH2CH2CH2-O-CH2CH2OH [화학식 5에서 R1=R2=R3=클로로, L1=L2=1,3-프로필렌, n=1, R11=수소에 해당]Si-4: (Cl) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CH 2 OH [Formula 5, R 1 = R 2 = R 3 = chloro, L 1 = L 2 = 1,3-propylene, n = 1, R 11 = corresponds to hydrogen]
Si-5 :
Figure PCTKR2018003652-appb-I000033
[화학식 4에서 R1=R2=R3=메톡시, L1=
Figure PCTKR2018003652-appb-I000034
, n=1, R11=수소에 해당]Si-5:
Figure PCTKR2018003652-appb-I000033
[Formula 4, R 1 = R 2 = R 3 = methoxy, L 1 =
Figure PCTKR2018003652-appb-I000034
, n = 1, R 11 = corresponds to hydrogen]
Si-6 : (EtO)3Si-CH2CH2-O-CH2CH2-O-(CH2CH2O)5-H [화학식 5에서 R1=R2=R3=에톡시, L1=L2=1,2-에틸렌, n=5, R11=수소에 해당]Si-6: (EtO) 3 Si-CH 2 CH 2 -O-CH 2 CH 2 -O- (CH 2 CH 2 O) 5 -H [In Formula 5, R 1 = R 2 = R 3 = Ethoxy, L 1 = L 2 = 1,2-ethylene, n = 5, R 11 = corresponds to hydrogen]
Si-7 : (EtO)3Si-CH2CH2CH2-O-CH2CH2CH2-O-(CH2CH2O)10-H [화학식 5에서 R1=R2=R3=에톡시, L1=L2=1,3-프로필렌, n=10, R11=수소에 해당] Si-7: (EtO) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O- (CH 2 CH 2 O) 10 -H [R 1 = R 2 = R 3 in the formula (5) = Ethoxy, L 1 = L 2 = 1,3-propylene, n = 10, R 11 = corresponds to hydrogen]
Si-8 : (EtO)3Si-CH2CH2CH2-O-CH2CH2CH2-O-CH2CH2O-CH3 [화학식 5에서 R1=R2=R3=에톡시, L1=L2=1,3-프로필렌, n=1, R11=메틸에 해당]Si-8: (EtO) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CH 2 O-CH 3 [In Formula 5, R 1 = R 2 = R 3 = Oxy, L 1 = L 2 = 1,3-propylene, n = 1, R 11 = corresponding to methyl]
Si-9 : (HO)3Si-CH2CH2CH2-O-CH2CH2CH2-O-CH2CH2O-CH3 [화학식 5에서 R1=R2=R3=히드록시, L1=L2=1,3-프로필렌, n=1, R11=메틸에 해당]Si-9: (HO) 3 Si-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 -O-CH 2 CH 2 O-CH 3 [Formula 5, R 1 = R 2 = R 3 = Hide Roxy, L 1 = L 2 = 1,3-propylene, n = 1, R 11 = Methyl]
Si-12 : (EtO)3Si-CH2CH2CH2-N[CH2CH2OH]2 [화학식 6에서 R1=R2=R3=에톡시, L1=1,3-프로필렌, n=y=1, R11=R12=수소에 해당]Si-12: (EtO) 3 Si-CH 2 CH 2 CH 2 -N [CH 2 CH 2 OH] 2 [Formula 6 R 1 = R 2 = R 3 = ethoxy, L 1 = 1,3-propylene , n = y = 1, R 11 = R 12 = corresponds to hydrogen]
Si-13 : (HO)3Si-CH2CH2CH2-N[CH2CH2OH]2 [화학식 6에서 R1=R2=R3=히드록시, L1=1,3-프로필렌, n=y=1, R11=R12=수소에 해당]Si-13: (HO) 3 Si-CH 2 CH 2 CH 2 -N [CH 2 CH 2 OH] 2 [Formula 6, wherein R 1 = R 2 = R 3 = hydroxy, L 1 = 1,3-propylene , n = y = 1, R 11 = R 12 = corresponds to hydrogen]
Si-14 : (Cl)3Si-CH2CH2CH2-N[CH2CH2OH]2 [화학식 6에서 R1=R2=R3=클로로, L1=1,3-프로필렌, n=y=1, R11=R12=수소에 해당]Si-14: (Cl) 3 Si-CH 2 CH 2 CH 2 -N [CH 2 CH 2 OH] 2 [Formula 6 R 1 = R 2 = R 3 = chloro, L 1 = 1,3-propylene, n = y = 1, R 11 = R 12 = corresponds to hydrogen]
Si-15 : (EtO)3Si-CH2CH2CH2-N(CH2CH2OH)-CH2CH2CH2-N[CH2CH2OH]2 [화학식 7에서 R1=R2=R3=에톡시, L1=L2=1,3-프로필렌, n=y=z=1, R11=R12=R13=수소에 해당]]Si-15: (EtO) 3 Si-CH 2 CH 2 CH 2 -N (CH 2 CH 2 OH) -CH 2 CH 2 CH 2 -N [CH 2 CH 2 OH] 2 [wherein R 1 = R 2 = R 3 = ethoxy, L 1 = L 2 = 1,3-propylene, n = y = z = 1, R 11 = R 12 = R 13 = corresponds to hydrogen]]
Si-16 : (EtO)3Si-CH2CH2CH2-N(CH2CH2OH)-CH2CH2CH2-N(CH2CH2OH)-CH2CH2CH2-N[CH2CH2OH]2 [화학식 8에서 R1=R2=R3=에톡시, L1=L2=L3=1,3-프로필렌, n=y=z=w=1, R11=R12=R13=R14=수소에 해당]Si-16: (EtO) 3 Si-CH 2 CH 2 CH 2 -N (CH 2 CH 2 OH) -CH 2 CH 2 CH 2 -N (CH 2 CH 2 OH) -CH 2 CH 2 CH 2 -N [CH 2 CH 2 OH] 2 [wherein R 1 = R 2 = R 3 = ethoxy, L 1 = L 2 = L 3 = 1,3-propylene, n = y = z = w = 1, R 11 = R 12 = R 13 = R 14 = corresponds to hydrogen]
Si-17 : (EtO)3Si-CH2CH2-NHCH2CH2OCH3 [화학식 6에서 R1=R2=R3=에톡시, L1=1,2-에틸렌, n=1, y=0, R11=메틸, R12=수소에 해당]Si-17: (EtO) 3 Si-CH 2 CH 2 -NHCH 2 CH 2 OCH 3 [wherein R 1 = R 2 = R 3 = ethoxy, L 1 = 1,2-ethylene, n = 1, y = 0, R 11 = methyl, R 12 = corresponds to hydrogen]
Si-18 : (EtO)3Si-CH2CH2CH2-N((CH2CH2O)5H)-CH2CH2CH2-N[(CH2CH2O)5H]2 [화학식 7에서 R1=R2=R3= 에톡시, L1=L2=1,3-프로필렌, n=y=z=5, R11=R12=R13=수소에 해당]Si-18: (EtO) 3 Si-CH 2 CH 2 CH 2 -N ((CH 2 CH 2 O) 5 H) -CH 2 CH 2 CH 2 -N [(CH 2 CH 2 O) 5 H] 2 [Formula 7 corresponds to R 1 = R 2 = R 3 = ethoxy, L 1 = L 2 = 1,3-propylene, n = y = z = 5, R 11 = R 12 = R 13 = hydrogen]
Si-19 : (EtO)3Si-CH2CH2CH2-N[(CH2CH2O)5CH3]2 [화학식 6에서 R1=R2=R3=에톡시, L1=1,3-프로필렌, n=y=5, R11=R12=메틸에 해당]Si-19: (EtO) 3 Si-CH 2 CH 2 CH 2 -N [(CH 2 CH 2 O) 5 CH 3 ] 2 [Formula 6 wherein R 1 = R 2 = R 3 = ethoxy, L 1 = 1,3-propylene, equivalent to n = y = 5, R 11 = R 12 = methyl]
[실시예 1 내지 10 및 비교예 1 내지 6] 실리콘 질화막 식각 조성물의 제조[Examples 1 to 10 and Comparative Examples 1 to 6] Preparation of Silicon Nitride Etch Composition
하기 표 1에 기재된 조성비로 혼합한 후 상온에서 5분간 500rpm의 속도로 교반하여 실리콘 질화막 식각 조성물을 제조하였다. 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 하였다. After mixing in the composition ratio shown in Table 1 and then stirred at a speed of 500rpm at room temperature for 5 minutes to prepare a silicon nitride film etching composition. The content of water was used as the balance so that the total weight of the composition was 100% by weight.
Figure PCTKR2018003652-appb-T000001
Figure PCTKR2018003652-appb-T000001
Figure PCTKR2018003652-appb-I000035
Figure PCTKR2018003652-appb-I000035
Figure PCTKR2018003652-appb-I000036
Figure PCTKR2018003652-appb-I000036
[실험예 1] 실리콘 질화막 및 실리콘 산화막의 식각량 및 식각 속도의 측정Experimental Example 1 Measurement of Etching Amount and Etch Rate of Silicon Nitride and Silicon Oxide
상기 실시예 및 비교예에서 제조된 실리콘 질화막 식각 조성물의 식각 성능을 알아보기 위하여 CVD 방법을 이용하여 반도체 제조 과정과 동일하게 증착하여 실리콘 질화막(SiN막) 웨이퍼 및 실리콘 산화막(열산화 막(thermal oxide) 또는 LP-TEOS(Low Pressure Tetra Ethyl Ortho Silicate)막) 웨이퍼를 각각 준비하였다.In order to examine the etching performance of the silicon nitride film etching composition prepared in the above Examples and Comparative Examples, the silicon nitride film (SiN film) wafer and the silicon oxide film (thermal oxide film) were deposited in the same manner as in the semiconductor manufacturing process using the CVD method. ) Or LP-TEOS (Low Pressure Tetra Ethyl Ortho Silicate) films were prepared, respectively.
식각을 시작하기 전, 박막 두께 측정 장비인 엘립소미터(Ellipsometer, J.A WOOLLAM社, M-2000U)를 이용하여 식각 전의 두께를 측정하였다. 석영 재질의 배쓰(bath)내에서 식각 온도 157℃로 유지되고 있는 실리콘 질화막 식각액(실시예 1 내지 20 및 비교예 1 내지 6)에 웨이퍼를 각 10분씩 담궈 식각 공정을 진행하였다. 식각이 완료된 후에 초순수로 세정한 후 건조 장치를 이용하여 잔여 식각액 및 수분을 완전히 건조시켰다. Before starting the etching, the thickness before etching was measured using an ellipsometer (M-2000U, J.A WOOLLAM, Inc.) which is a thin film thickness measuring instrument. The etching process was performed by dipping the wafer into the silicon nitride film etching solution (Examples 1 to 20 and Comparative Examples 1 to 6) maintained at an etching temperature of 157 ° C. in a quartz bath for 10 minutes. After the etching was completed, the resultant was washed with ultrapure water, and the remaining etchant and moisture were completely dried using a drying apparatus.
식각 속도는 엘립소미터(Ellipsometer, J.A WOOLLAM社, M-2000U)를 이용하여 식각 전의 두께와 식각 후의 두께의 차이를 식각 시간(분)으로 나누어 산출하였으며, 그 결과를 하기 표 2에 기재하였다.The etching rate was calculated by dividing the difference between the thickness before etching and the thickness after etching using an ellipsometer (J.A WOOLLAM, M-2000U) by etching time (minutes), and the results are shown in Table 2 below.
[실험예 2] 실리콘 산화막에 대한 실리콘 질화막의 선택적 식각 평가Experimental Example 2 Evaluation of Selective Etching of Silicon Nitride on Silicon Oxide
실리콘 질화막의 식각 속도와 실리콘 산화막의 식각 속도의 비에 의해 식각 선택비(실리콘 질화막의 식각 속도/실리콘 산화막의 식각 속도)를 계산하여 하기 표 2에 기재하였다.The etching selectivity (the etching rate of the silicon nitride film / the etching rate of the silicon oxide film) was calculated according to the ratio of the etching rate of the silicon nitride film and the etching rate of the silicon oxide film, and is shown in Table 2 below.
[실험예 3] 파티클 발생 정도 평가Experimental Example 3 Particle Generation Evaluation
상기 실시예 1 내지 20 및 비교예 1 내지 6에서 식각된 실리콘 산화막의 표면을 전자 주사 현미경(SEM)으로 측정하여 파티클의 발생 여부를 검사하여 하기 표 2에 기재하였다.The surface of the silicon oxide film etched in Examples 1 to 20 and Comparative Examples 1 to 6 was measured by an electron scanning microscope (SEM) to examine whether particles were generated, and are described in Table 2 below.
Figure PCTKR2018003652-appb-T000002
Figure PCTKR2018003652-appb-T000002
상기 표 2에 기재된 바와 같이, 실시예 1 내지 20의 실리콘 질화막 식각 조성물은 실리콘 질화막에 대한 우수한 식각 속도를 나타냄과 동시에 실리콘 산화막의 종류에 상관없이 낮은 식각 속도를 나타내어 결과적으로 우수한 식각 선택비를 나타내었고, 또한, 파티클 발생을 효과적으로 방지하였다.As shown in Table 2, the silicon nitride film etching compositions of Examples 1 to 20 exhibited excellent etching rates with respect to the silicon nitride films and low etching rates regardless of the types of silicon oxide films, resulting in excellent etching selectivity. In addition, particle generation was effectively prevented.
그러나, 비교예 1 및 2의 실리콘 질화막 식각 조성물은 실리콘 산화막 식각 억제력이 현저하게 떨어지고, 결과적으로 낮은 식각 선택비를 나타내었을 뿐만 아니라 파티클이 생성되어 실리콘 질화막을 선택적 및 안정적으로 식각하는데 부적합하였다. 또한, 비교예 3의 실리콘 질화막 식각 조성물은 식각 공정 중 파티클이 발생되지는 않았으나, 실리콘 질화막에 대한 식각 선택비가 매우 낮아 실리콘 질화막을 선택적으로 식각하는데 부적합하였다. 또한, 비교예 4 내지 6의 실리콘 질화막 식각 조성물은 높은 식각 선택비를 나타내었으나, 식각 공정 중 부반응으로 인해 파티클이 발생되어 실리콘 질화막을 안정적으로 식각하는데 부적합하였다.However, the silicon nitride film etching compositions of Comparative Examples 1 and 2 had a significant drop in silicon oxide etch inhibition, resulting in a low etching selectivity, and particles were not suitable for selectively and stably etching the silicon nitride film. In addition, although the silicon nitride film etching composition of Comparative Example 3 did not generate particles during the etching process, the etching selectivity with respect to the silicon nitride film was very low, and thus was not suitable for selectively etching the silicon nitride film. In addition, although the silicon nitride film etching compositions of Comparative Examples 4 to 6 exhibited high etching selectivity, particles were generated due to side reactions during the etching process, and thus, were not suitable for stably etching the silicon nitride film.
즉, 실시예 1 내지 20의 실리콘 질화막 식각 조성물은 규소계 화합물을 포함하지 않는 비교예 1 내지 3의 실리콘 질화막 식각 조성물에 비해 실리콘 산화막 식각 속도가 현저하게 감소하였다. 따라서, 상기 화학식 1의 규소계 화합물을 실리콘 질화막 식각 조성물에 포함하는 경우 실리콘 산화막의 식각을 현저하게 억제하여 실리콘 산화막에 대한 실리콘 질화막의 식각 선택비가 현저하게 높아짐을 알 수 있었다.That is, in the silicon nitride film etching compositions of Examples 1 to 20, the silicon oxide film etching rate was significantly reduced compared to the silicon nitride film etching compositions of Comparative Examples 1 to 3 that do not include the silicon-based compound. Therefore, when the silicon-based compound of Formula 1 is included in the silicon nitride film etching composition, it was found that the etching selectivity of the silicon nitride film to the silicon oxide film is significantly increased by significantly suppressing the etching of the silicon oxide film.
또한, 실시예 1 내지 10의 실리콘 질화막 식각 조성물은 말단에 에틸렌옥사이드 반복 단위가 적어도 하나 결합되고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 수소가 결합되거나, 알킬과 같은 탄화수소 기가 결합된 규소계 화합물을 포함하고 있고, 실시예 11 내지 20의 실리콘 질화막 식각 조성물은 말단 질소 원자에 에틸렌옥사이드 반복 단위가 적어도 하나 결합되고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 수소가 결합되거나, 알킬과 같은 탄화수소 기가 결합된 규소계 화합물을 포함하고 있어 APTES, HPST 및 THSPS을 각각 포함하는 비교예 4 내지 6에 비해 식각 공정 중 발생하는 파티클의 생성을 효과적으로 방지하였다.In the silicon nitride film etching compositions of Examples 1 to 10, at least one ethylene oxide repeating unit is bonded at a terminal thereof, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit or a hydrocarbon group such as alkyl is bonded. In the silicon nitride film etching composition of Examples 11 to 20, at least one ethylene oxide repeating unit is bonded to a terminal nitrogen atom, hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon group such as alkyl is used. Including the bonded silicon-based compound effectively prevented the generation of particles generated during the etching process compared to Comparative Examples 4 to 6 containing APTES, HPST and THSPS, respectively.
즉, 본 발명의 실리콘 질화막 식각 조성물에 포함되는 상기 화학식 1의 규소계 화합물은 고온의 산 조건에서 매우 안정적이므로, 식각 공정시 고온으로 가열된 인산이 실리콘 산화막을 식각하는 것을 효율적으로 억제함과 동시에 부반응의 발생을 막아 종래 문제시되었던 파티클의 발생을 완벽하게 방지할 수 있어 기판의 불량 없이 실리콘 질화막을 고선택적으로 식각할 수 있고, 공정의 안정성 및 신뢰성을 확보할 수 있었다. That is, since the silicon-based compound of Formula 1 included in the silicon nitride film etching composition of the present invention is very stable under high temperature acid conditions, the phosphoric acid heated to high temperature during the etching process effectively inhibits etching of the silicon oxide film. By preventing side reactions, it is possible to completely prevent generation of particles, which has been a problem in the past, and thus to selectively etch the silicon nitride film without defect of the substrate, and to secure process stability and reliability.
따라서, 본 발명에 따른 실리콘 질화막 식각 조성물은 질화막 식각 시 산화막의 막질 손상이나 산화막의 식각으로 인한 전기적 특성 저하 및 파티클 발생을 방지하면서 질화막을 선택적으로 식각함으로써, 소자 특성을 향상시킬 수 있다.Therefore, the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
상기 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다는 것이 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 명백할 것이다.The present invention is not limited to the above-described embodiment and the accompanying drawings, and it is common in the art that various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It will be apparent to those who have knowledge.
본 발명의 실리콘 질화막 식각 조성물은 실리콘 산화막의 식각을 억제하고, 실리콘 질화막을 높은 선택성으로 식각할 수 있고, 실리콘 산화막의 데미지를 최소화하고, 파티클 발생을 효과적으로 방지하여, 식각 공정에서 원치 않는 손상을 방지할 수 있기 때문에 제조된 소자 특성이 저하되는 문제를 방지할 수 있다. The silicon nitride film etching composition of the present invention can suppress the etching of the silicon oxide film, can etch the silicon nitride film with high selectivity, minimize the damage of the silicon oxide film, and effectively prevent the generation of particles, thereby preventing unwanted damage in the etching process Since it is possible to prevent the problem of deteriorating the produced device characteristics.
또한 본 발명의 실리콘 질화막 식각 조성물은 에틸렌옥사이드(Ethylene oxide, EO) 반복 단위가 적어도 하나 결합되고, 상기 에틸렌 옥사이드 반복단위의 말단 산소 원자에 수소가 결합되거나, 알킬, 사이클로알킬 또는 알케닐과 같은 탄화수소 기가 결합된 구조의 안정적인 규소계 화합물을 포함하고 있으므로, 식각 공정에서 상기 규소계 화합물의 안정성으로 인하여 고온으로 가열된 인산이 상기 실리콘 산화막을 식각하지 못하도록 하면서, 상기 규소계 화합물의 부반응을 막아 파티클의 발생 없이 실리콘 질화막을 선택적으로 식각할 수 있도록 한다. 따라서, 본 발명에 따른 실리콘 질화막 식각 조성물은 질화막 식각 시 산화막의 막질 손상이나 산화막의 식각으로 인한 전기적 특성 저하 및 파티클 발생을 방지하면서 질화막을 선택적으로 식각함으로써, 소자 특성을 향상시킬 수 있다.In the silicon nitride film etching composition of the present invention, at least one ethylene oxide (EO) repeating unit is bonded, and hydrogen is bonded to a terminal oxygen atom of the ethylene oxide repeating unit, or a hydrocarbon such as alkyl, cycloalkyl or alkenyl. Since the group includes a stable silicon compound having a bonded structure, the phosphoric acid heated to a high temperature does not etch the silicon oxide layer due to the stability of the silicon compound in the etching process, and prevents side reactions of the silicon compound to prevent etching of the particles. The silicon nitride film can be selectively etched without generation. Therefore, the silicon nitride film etching composition according to the present invention can improve device characteristics by selectively etching the nitride film while preventing the deterioration of electrical properties and particle generation due to the film quality damage of the oxide film or the etching of the oxide film during etching of the nitride film.
또한, 본 발명의 실리콘 질화막 식각 조성물은 보관 안정성이 우수하고, 반복적인 식각 공정 후에도 실리콘 질화막에 대한 안정적인 식각속도 및 높은 식각 선택성을 유지할 수 있다.In addition, the silicon nitride film etching composition of the present invention is excellent in storage stability, and can maintain a stable etching rate and high etching selectivity to the silicon nitride film even after repeated etching processes.

Claims (10)

  1. 인산; 및Phosphoric acid; And
    하기 화학식 1로 표시되는 규소계 화합물; 포함하는 실리콘 질화막 식각 조성물.Silicon-based compounds represented by Formula 1 below; Silicon nitride film etching composition comprising.
    [화학식 1][Formula 1]
    Figure PCTKR2018003652-appb-I000037
    Figure PCTKR2018003652-appb-I000037
    상기 화학식 1에서,In Chemical Formula 1,
    R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐 또는
    Figure PCTKR2018003652-appb-I000038
    이고;    R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or
    Figure PCTKR2018003652-appb-I000038
    ego;
    L 및 L1은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
    L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
    Q는 -O- 또는 -N[(CH2CH2O)y-R12]-이며;Q is -O- or -N [(CH 2 CH 2 O) y -R 12 ]-;
    A는 -O- 또는 -N[(CH2CH2O)z-R13]-이고;A is -O- or -N [(CH 2 CH 2 O) z -R 13 ]-;
    R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
    n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
    x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
    y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
    L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
    Q'는 -O- 또는 -N[(CH2CH2O)c-R22]-이며;Q 'is -O- or -N [(CH 2 CH 2 O) c -R 22 ]-;
    A'는 -O- 또는 -N[(CH2CH2O)d-R23]-이고;A 'is -O- or -N [(CH 2 CH 2 O) d -R 23 ]-;
    R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
    b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
  2. 제 1항에 있어서,The method of claim 1,
    상기 규소계 화합물은 하기 화학식 2 또는 화학식 3으로 표시되는 규소계 화합물인 실리콘 질화막 식각 조성물.The silicon compound is a silicon nitride film etching composition is a silicon compound represented by the following formula (2) or (3).
    [화학식 2][Formula 2]
    Figure PCTKR2018003652-appb-I000039
    Figure PCTKR2018003652-appb-I000039
    [화학식 3][Formula 3]
    Figure PCTKR2018003652-appb-I000040
    Figure PCTKR2018003652-appb-I000040
    상기 화학식 2 및 3에서,In Chemical Formulas 2 and 3,
    R1 내지 R3는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 2 내지 10의 알케닐,
    Figure PCTKR2018003652-appb-I000041
    또는
    Figure PCTKR2018003652-appb-I000042
    이고;    R 1 to R 3 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms,
    Figure PCTKR2018003652-appb-I000041
    or
    Figure PCTKR2018003652-appb-I000042
    ego;
    L 및 L1은 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L and L 1 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or-(CH 2 ) x -L 3- ;
    L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is cycloalkylene having 3 to 8 carbon atoms;
    R11 내지 R13는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 13 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    m은 0 내지 5의 정수이고, 상기 m이 2 이상의 정수인 경우 L은 서로 동일하거나 상이할 수 있고, A는 서로 동일하거나 상이할 수 있고,m is an integer of 0 to 5, when m is an integer of 2 or more, L may be the same or different from each other, A may be the same or different from each other,
    n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
    x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
    y 및 z는 각각 독립적으로 0 내지 20의 정수이고;y and z are each independently an integer from 0 to 20;
    L' 및 L1'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 'and L 1 ' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
    R21 내지 R23는 각각 독립적으로 수소, 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    a는 0 내지 5의 정수이고, 상기 a가 2 이상의 정수인 경우 L'은 서로 동일하거나 상이할 수 있고, A'는 서로 동일하거나 상이할 수 있고,a is an integer of 0 to 5, when a is an integer of 2 or more, L 'may be the same or different from each other, A' may be the same or different from each other,
    b, c 및 d는 각각 독립적으로 0 내지 20의 정수이다.b, c and d are each independently an integer of 0 to 20.
  3. 제 2항에 있어서,The method of claim 2,
    상기 규소계 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 규소계 화합물인 실리콘 질화막 식각 조성물.The silicon compound is a silicon nitride film etching composition is a silicon compound represented by the following formula (4) or (5).
    [화학식 4][Formula 4]
    Figure PCTKR2018003652-appb-I000043
    Figure PCTKR2018003652-appb-I000043
    [화학식 5][Formula 5]
    Figure PCTKR2018003652-appb-I000044
    Figure PCTKR2018003652-appb-I000044
    상기 화학식 4 및 5에서,In Chemical Formulas 4 and 5,
    R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시,
    Figure PCTKR2018003652-appb-I000045
    또는
    Figure PCTKR2018003652-appb-I000046
    이고;     R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms,
    Figure PCTKR2018003652-appb-I000045
    or
    Figure PCTKR2018003652-appb-I000046
    ego;
    L1 및 L2는 각각 독립적으로 탄소수 1 내지 10의 알킬렌, 탄소수 3 내지 8의 사이클로알킬렌 또는 -(CH2)x-L3- 이며;L 1 and L 2 are each independently alkylene having 1 to 10 carbon atoms, cycloalkylene having 3 to 8 carbon atoms, or — (CH 2 ) x —L 3 —;
    L3는 탄소수 3 내지 8의 사이클로알킬렌이며;L 3 is a cycloalkylene having 3 to 8 carbon atoms;
    R11은 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 is hydrogen, alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or alkenyl of 2 to 10 carbon atoms;
    n은 1 내지 20의 정수이고;n is an integer from 1 to 20;
    x는 1 내지 10의 정수이고;x is an integer from 1 to 10;
    L1' 및 L2'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 ′ and L 2 ′ are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
    R31 및 R32은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 31 and R 32 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    b는 0 내지 20의 정수이다.b is an integer of 0-20.
  4. 제 3항에 있어서,The method of claim 3, wherein
    상기 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1 및 L2는 각각 독립적으로 탄소수 1 내지 7의 알킬렌, 탄소수 5 내지 7의 사이클로알킬렌 또는 -(CH2)x-L3- 이며; L3는 탄소수 5 내지 7의 사이클로알킬렌이며; R11은 수소 또는 탄소수 1 내지 7의 알킬이고; n은 1 내지 10의 정수이고; x는 2 내지 7의 정수인, 실리콘 질화막 식각 조성물.R 1 to R 3 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 and L 2 are each independently alkylene having 1 to 7 carbon atoms, cycloalkylene having 5 to 7 carbon atoms, or — (CH 2 ) x —L 3 —; L 3 is cycloalkylene having 5 to 7 carbon atoms; R 11 is hydrogen or alkyl of 1 to 7 carbon atoms; n is an integer from 1 to 10; x is an integer of 2 to 7, silicon nitride film etching composition.
  5. 제 2항에 있어서,The method of claim 2,
    상기 규소계 화합물은 하기 화학식 6, 화학식 7 또는 화학식 8로 표시되는 규소계 화합물인 실리콘 질화막 식각 조성물.The silicon compound is a silicon nitride film etching composition is a silicon compound represented by the following formula (6), (7) or (8).
    [화학식 6][Formula 6]
    Figure PCTKR2018003652-appb-I000047
    Figure PCTKR2018003652-appb-I000047
    [화학식 7][Formula 7]
    Figure PCTKR2018003652-appb-I000048
    Figure PCTKR2018003652-appb-I000048
    [화학식 8][Formula 8]
    Figure PCTKR2018003652-appb-I000049
    Figure PCTKR2018003652-appb-I000049
    상기 화학식 6 내지 8에서,In Chemical Formulas 6 to 8,
    R1 내지 R3는 각각 독립적으로 할로겐, 히드록시, 탄소수 1 내지 10의 알콕시 또는
    Figure PCTKR2018003652-appb-I000050
    이고;    R 1 to R 3 are each independently halogen, hydroxy, alkoxy having 1 to 10 carbon atoms, or
    Figure PCTKR2018003652-appb-I000050
    ego;
    L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 , L 2 and L 3 are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
    R11 내지 R14는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 11 to R 14 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    n는 1 내지 20의 정수이고;n is an integer from 1 to 20;
    y는 0 내지 20의 정수이고;y is an integer from 0 to 20;
    w 및 z는 각각 독립적으로 1 내지 20의 정수이고;w and z are each independently an integer from 1 to 20;
    L1' 및 L'은 각각 독립적으로 탄소수 1 내지 10의 알킬렌 또는 탄소수 3 내지 8의 사이클로알킬렌이며;L 1 'and L' are each independently alkylene having 1 to 10 carbon atoms or cycloalkylene having 3 to 8 carbon atoms;
    R21 내지 R23은 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬, 탄소수 3 내지 8의 사이클로알킬 또는 탄소수 2 내지 10의 알케닐이고;R 21 to R 23 are each independently hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkenyl having 2 to 10 carbon atoms;
    b, c 및 d는 각각 독립적으로 0 내지 20의 정수이고;b, c and d are each independently an integer from 0 to 20;
    a은 0 내지 2의 정수이다.a is an integer of 0-2.
  6. 제 5항에 있어서,The method of claim 5,
    상기 R1 내지 R3는 각각 독립적으로 할로겐, 히드록시 또는 탄소수 1 내지 7의 알콕시이고; L1, L2 및 L3은 각각 독립적으로 탄소수 1 내지 7의 알킬렌 또는 탄소수 5 내지 7의 사이클로알킬렌이며; R11 내지 R14는 각각 독립적으로 수소 또는 탄소수 1 내지 7의 알킬이고; n는 1 내지 5의 정수이고; y는 0 내지 5의 정수이고; w 및 z는 각각 독립적으로 1 내지 5의 정수인, 실리콘 질화막 식각 조성물.R 1 to R 3 are each independently halogen, hydroxy or alkoxy having 1 to 7 carbon atoms; L 1 , L 2 and L 3 are each independently alkylene having 1 to 7 carbon atoms or cycloalkylene having 5 to 7 carbon atoms; R 11 to R 14 are each independently hydrogen or alkyl having 1 to 7 carbon atoms; n is an integer from 1 to 5; y is an integer from 0 to 5; w and z are each independently an integer of 1 to 5, the silicon nitride film etching composition.
  7. 제 1항에 있어서, The method of claim 1,
    상기 실리콘 질화막 식각 조성물은 상기 실리콘 질화막 식각 조성물 총 중량에 대하여 인산 60 내지 95 중량% 및 규소계 화합물 0.01 내지 3 중량%을 포함하는, 실리콘 질화막 식각 조성물. The silicon nitride film etching composition comprises 60 to 95% by weight of phosphoric acid and 0.01 to 3% by weight of the silicon compound based on the total weight of the silicon nitride film etching composition, silicon nitride film etching composition.
  8. 제 1항에 있어서,The method of claim 1,
    상기 실리콘 질화막 식각 조성물의 실리콘 질화막/산화막 식각 선택비는 200 이상인, 실리콘 질화막 식각 조성물.The silicon nitride film etching composition ratio of the silicon nitride film etching composition is 200 or more, silicon nitride film etching composition.
  9. 제 1항 내지 제 8항에서 선택되는 어느 한 항의 실리콘 질화막 식각 조성물을 이용하여 실리콘 산화막 대비 실리콘 질화막을 선택적으로 식각하는 방법.A method of selectively etching a silicon nitride film relative to a silicon oxide film using the silicon nitride film etching composition of any one of claims 1 to 8.
  10. 제 1항 내지 제 8항에서 선택되는 어느 한 항의 실리콘 질화막 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조 방법.The method of manufacturing a semiconductor device comprising an etching process performed using the silicon nitride film etching composition of any one of claims 1 to 8.
PCT/KR2018/003652 2017-03-28 2018-03-28 Silicon nitride film etching composition WO2018182307A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198935A1 (en) * 2018-04-11 2019-10-17 삼성에스디아이 주식회사 Silicon nitride film etching composition and etching method using same
CN111825709A (en) * 2019-04-18 2020-10-27 Sk新技术株式会社 Silicon compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120122037A1 (en) * 2009-07-23 2012-05-17 Bradford Michael L Method And Materials For Reverse Patterning
KR20130042273A (en) * 2011-10-18 2013-04-26 삼성전자주식회사 Compositions for etching and methods for forming semiconductor memory devices using the same
KR20160040436A (en) * 2014-10-03 2016-04-14 신에쓰 가가꾸 고교 가부시끼가이샤 Composition for forming a coating type silicon-containing film, substrate, and method for forming patterns
KR20160077937A (en) * 2014-12-24 2016-07-04 솔브레인 주식회사 Composition for etching and manufacturing method of semiconductor device using the same
KR20170001801A (en) * 2015-06-25 2017-01-05 오씨아이 주식회사 Etching solution for silicon nitride layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120122037A1 (en) * 2009-07-23 2012-05-17 Bradford Michael L Method And Materials For Reverse Patterning
KR20130042273A (en) * 2011-10-18 2013-04-26 삼성전자주식회사 Compositions for etching and methods for forming semiconductor memory devices using the same
KR20160040436A (en) * 2014-10-03 2016-04-14 신에쓰 가가꾸 고교 가부시끼가이샤 Composition for forming a coating type silicon-containing film, substrate, and method for forming patterns
KR20160077937A (en) * 2014-12-24 2016-07-04 솔브레인 주식회사 Composition for etching and manufacturing method of semiconductor device using the same
KR20170001801A (en) * 2015-06-25 2017-01-05 오씨아이 주식회사 Etching solution for silicon nitride layer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198935A1 (en) * 2018-04-11 2019-10-17 삼성에스디아이 주식회사 Silicon nitride film etching composition and etching method using same
CN111825709A (en) * 2019-04-18 2020-10-27 Sk新技术株式会社 Silicon compounds

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