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WO2018182307A1 - Composition de gravure de film de nitrure de silicium - Google Patents

Composition de gravure de film de nitrure de silicium 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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English (en)
Korean (ko)
Inventor
김동현
박현우
이명호
송명근
정진배
Original Assignee
주식회사 이엔에프테크놀로지
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Priority claimed from KR1020180035260A external-priority patent/KR102240654B1/ko
Priority claimed from KR1020180035221A external-priority patent/KR102240647B1/ko
Application filed by 주식회사 이엔에프테크놀로지 filed Critical 주식회사 이엔에프테크놀로지
Publication of WO2018182307A1 publication Critical patent/WO2018182307A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Weting (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

La présente invention concerne une composition de gravure de film de nitrure de silicium qui peut réduire au minimum la vitesse de gravure d'un film d'oxyde de silicium, peut graver sélectivement un film de nitrure de silicium, ne laisse aucune particule sur un substrat et est stable à une température élevée.
PCT/KR2018/003652 2017-03-28 2018-03-28 Composition de gravure de film de nitrure de silicium WO2018182307A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR20170039127 2017-03-28
KR10-2017-0039127 2017-03-28
KR10-2017-0039106 2017-03-28
KR20170039106 2017-03-28
KR1020180035260A KR102240654B1 (ko) 2017-03-28 2018-03-27 실리콘 질화막 식각 조성물
KR10-2018-0035221 2018-03-27
KR10-2018-0035260 2018-03-27
KR1020180035221A KR102240647B1 (ko) 2017-03-28 2018-03-27 실리콘 질화막 식각 조성물

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198935A1 (fr) * 2018-04-11 2019-10-17 삼성에스디아이 주식회사 Composition de gravure de film de nitrure de silicium et procédé de gravure l'utilisant
CN111825709A (zh) * 2019-04-18 2020-10-27 Sk新技术株式会社 硅化合物

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US20120122037A1 (en) * 2009-07-23 2012-05-17 Bradford Michael L Method And Materials For Reverse Patterning
KR20130042273A (ko) * 2011-10-18 2013-04-26 삼성전자주식회사 식각용 조성물 및 이를 이용하는 반도체 기억 소자의 형성 방법
KR20160040436A (ko) * 2014-10-03 2016-04-14 신에쓰 가가꾸 고교 가부시끼가이샤 도포형 규소 함유막 형성용 조성물, 기판, 및 패턴형성방법
KR20160077937A (ko) * 2014-12-24 2016-07-04 솔브레인 주식회사 식각 조성물 및 이를 이용한 반도체 소자의 제조방법
KR20170001801A (ko) * 2015-06-25 2017-01-05 오씨아이 주식회사 실리콘 질화막 식각 용액

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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 (ko) * 2011-10-18 2013-04-26 삼성전자주식회사 식각용 조성물 및 이를 이용하는 반도체 기억 소자의 형성 방법
KR20160040436A (ko) * 2014-10-03 2016-04-14 신에쓰 가가꾸 고교 가부시끼가이샤 도포형 규소 함유막 형성용 조성물, 기판, 및 패턴형성방법
KR20160077937A (ko) * 2014-12-24 2016-07-04 솔브레인 주식회사 식각 조성물 및 이를 이용한 반도체 소자의 제조방법
KR20170001801A (ko) * 2015-06-25 2017-01-05 오씨아이 주식회사 실리콘 질화막 식각 용액

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198935A1 (fr) * 2018-04-11 2019-10-17 삼성에스디아이 주식회사 Composition de gravure de film de nitrure de silicium et procédé de gravure l'utilisant
CN111825709A (zh) * 2019-04-18 2020-10-27 Sk新技术株式会社 硅化合物

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