WO2020122454A1 - Agent de gravure hautement sélectif pour semi-conducteur, agent de gravure sélectif pour film de nitrure de silicium et fabrication de dispositif à semi-conducteur faisant appel à ceux-ci - Google Patents

Agent de gravure hautement sélectif pour semi-conducteur, agent de gravure sélectif pour film de nitrure de silicium et fabrication de dispositif à semi-conducteur faisant appel à ceux-ci Download PDF

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WO2020122454A1
WO2020122454A1 PCT/KR2019/016069 KR2019016069W WO2020122454A1 WO 2020122454 A1 WO2020122454 A1 WO 2020122454A1 KR 2019016069 W KR2019016069 W KR 2019016069W WO 2020122454 A1 WO2020122454 A1 WO 2020122454A1
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Prior art keywords
nitride film
silicon nitride
acid
silicon
etching solution
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PCT/KR2019/016069
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English (en)
Korean (ko)
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정경진
윤영록
한재희
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주식회사 케이씨텍
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Priority claimed from KR1020190060753A external-priority patent/KR102307189B1/ko
Priority claimed from KR1020190092999A external-priority patent/KR102278765B1/ko
Application filed by 주식회사 케이씨텍 filed Critical 주식회사 케이씨텍
Publication of WO2020122454A1 publication Critical patent/WO2020122454A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means

Definitions

  • the present invention relates to a high selectivity etchant for semiconductors, a selective etching solution for silicon nitride films, and a method of manufacturing a semiconductor device using the same.
  • various insulating films such as a silicon oxide film and a silicon nitride film can be stacked on a substrate. According to the needs of forming various patterns included in the semiconductor device, there is a need for a selective etching process of the silicon nitride film.
  • an etching composition having an acid component may be used, and the etching composition should have a high selectivity to the conductive film without damaging an insulating film structure such as an oxide film. It is necessary to maintain a uniform etching characteristic while the etching process is performed. As the etching process progresses, the etching rate may decrease and the selectivity of the silicon nitride film to silicon oxide film may also decrease.
  • the existing silicon nitride/oxide selection ratio control technology is a method of reducing the etching ability of the oxide film by increasing the silicon concentration by dissolving the silicate-based compound in the etching solution, and adding a silane-based compound to protect the oxide film surface to suppress etching
  • it is advantageous for growth it is often difficult to implement a high selectivity ratio of 1000: 1 or higher before the use of a silane-based compound, or because a pre-reaction is required or the etching inhibitory effect is low.
  • Korean Patent Publication No. 10-2005-0003163 discloses an etching solution for nitride films of semiconductor devices containing phosphoric acid and hydrofluoric acid.
  • hydrofluoric acid is included in the etching solution, the silicon oxide film is also removed, and thus it is difficult to secure a sufficient etching selectivity of the nitride film compared to the oxide film.
  • Silicon oxide film (SiO 2 ) and silicon nitride film (SiNx) are typical insulating films used in semiconductor manufacturing processes. These may be used alone or may be used in which one or more silicon oxide films and one or more silicon nitride films are alternately stacked. It is also used as a hard mask for forming a conductive pattern such as metal wiring.
  • an acid-based etching solution is generally used, and the etching solution is required to have a high selectivity to the silicon nitride film without damaging the silicon oxide film.
  • the selectivity was adjusted by adding a silane-based compound to the etching solution to protect the surface of the oxide film, or by dissolving the silicate-based compound in the etching solution to increase the silicon concentration to decrease the etching ability.
  • the present invention is to solve the above-mentioned problems, the object of the present invention is to selectively remove the silicon nitride film and at the same time minimize the etch rate of the silicon oxide film, to solve problems such as foreign matter generation adversely affecting semiconductor device characteristics It is to provide a method for manufacturing a silicon nitride film etching composition having a high selectivity and a semiconductor device using the same.
  • the object of the present invention is to selectively remove the silicon nitride film while minimizing the etching of the silicon oxide film, as well as to suppress the generation of particles to suppress the occurrence of abnormal growth in the semiconductor device silicon nitride film selective etching solution and using the same It is to provide a method for manufacturing a semiconductor device.
  • a high selectivity etchant for semiconductors includes an inorganic acid; Silane-based regulators; And Sulfur-based adjuvants.
  • the silane-based modulator may be one containing an alkyl group or an amino group having 1 to 3 carbon atoms.
  • the silane-based regulator may be one containing one to three alkyl groups.
  • the silane-based modulator may include 1 to 6 alkoxy groups, and the alkoxy group may be a methoxy group or an ethoxy group.
  • the silane-based modulator 3-Aminopropyl (diethoxy) methylsilane, 3- (2-aminoethylamino) propyl triethoxysilane (3- (2 -Aminoethylamino)propyldimethoxymethylsilane, 3-Aminopropyldimethoxymethylsilane, Diethoxydimethylsilane, Diethoxydiphenylsilane, (3-aminopropyl)triethoxysilane ((3 -Aminopropyl)triethoxysilane), (3-glycidyloxypropyl)trimethoxysilane, (Vinyltrimethoxysilane), N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane (N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane), 3-Aminopropyltrimethoxys
  • the content of the silane-based regulator in the high selectivity etchant for semiconductors may be from 0.01% to 1% by weight.
  • the sulfur (Sulfur)-based adjuvant sulfate (Sulfate), hydrogen sulfate (HydrogenSulfate), peroxide (Persulfate), sulfite (Sulfite), bisulfite (bisulfite), hyposulfate (Hyposulfite), hydro Sulfur containing at least one salt selected from the group consisting of hydrosulfite, metabisulfite, thiosulfate, sulfur dioxide, sulfur trioxide and sulfuric acid Sulfur).
  • the Sulfur-based adjuvant Ammonium sulfate, Ammonium bisulfite, Ammonium hydrosulfide, Ammonium metabisulfite, Ammonium Sulfite ) And ammonium persulfate (Ammonium persulfate).
  • the content of the sulfur-based auxiliary agent may be 0.05 to 5% by weight.
  • the inorganic acid may include at least one selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphorous acid, metaphosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, nitric acid and nitrous acid.
  • the content of the inorganic acid in the high selectivity etchant for semiconductors may be 85 to 90% by weight.
  • the silicon concentration in the high selectivity etchant for semiconductors according to Equation 1 below may be 50 ppm to 1500 ppm.
  • the etch selectivity of the silicon nitride film to the silicon oxide film may be 80:1 to 8000:1.
  • An etching method of a substrate on which a silicon oxide film and a silicon nitride film are formed according to another embodiment of the present invention includes forming a silicon oxide film and a silicon nitride film on a substrate; And etching the substrate on which the silicon oxide film and the silicon nitride film are formed using a high selectivity etchant for semiconductors, wherein the high selectivity etchant for semiconductors is high selectivity for semiconductors according to an embodiment of the present invention. It is a non-etching liquid.
  • the inorganic acid A silicon-based compound represented by Formula 2 below; And water; to provide a silicon nitride film selective etching solution.
  • L is a single bond, alkylene having 1 to 10 carbons or cycloalkylene having 4 to 8 carbons, R1 is hydrogen, hydroxy, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, R2 is hydroxy, Alcohol having 1 to 10 carbon atoms or alkoxy having 1 to 10 carbon atoms, and n is an integer of 1 to 10 carbon atoms.
  • L is alkylene having 1 to 10 carbons or cycloalkylene having 4 to 8 carbons
  • R1 is hydrogen, hydroxy or alkyl having 1 to 6 carbons
  • R2 is hydroxy
  • n may be an integer of 1 to 5.
  • L may be alkylene having 1 to 5 carbons
  • R1 is hydrogen or alkyl having 1 to 5 carbons
  • R2 is hydroxy
  • n may be an integer of 1 to 3.
  • the silicon-based compound represented by Chemical Formula 2 is 3-(trihydroxysilyl)propyl sulfamic acid, methyl (3-(trihydroxysilyl)propyl) sulfamic acid, 3-(3- (Trihydroxysilyl)propylamino)propylsulfamic acid, 3-(3-(trihydroxysilyl)propylamino)propylsulfamic acid, 3-(3-(3-(trihydroxysilyl)propylamino) Propylamino)propylsulfamic acid and methyl(3-(methyl(3-(methyl(3-(trihydroxysilyl)propyl)amino)propyl)amino)propyl)sulphamic acid.
  • the inorganic acid may include at least one selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphorous acid, metaphosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, nitric acid and nitrous acid.
  • the content of the inorganic acid may be 85 to 90% by weight.
  • the content of the silicon-based compound represented by Chemical Formula 2 in the silicon nitride film selective etching solution may be 0.01 wt% to 3 wt%.
  • the inorganic acid is 85% by weight to 90% by weight
  • the silicon-based compound represented by Chemical Formula 2 may be 0.01% by weight to 3% by weight, and may include residual water.
  • the silicon nitride film selective etching solution may have a selection ratio of a silicon nitride film to a silicon oxide film of 100:1 or more.
  • the silicon nitride film selective etching solution the etching rate for the silicon nitride film is 400 to 500 Is, the etching rate for the silicon oxide film is 3 It may be the following.
  • the silicon nitride film selective etching solution may be to suppress particle generation during an etching process.
  • Another aspect of the present invention forming a silicon oxide film and a silicon nitride film on a substrate; And etching the substrate on which the silicon oxide film and the silicon nitride film are formed using a silicon nitride film selective etching solution, wherein the silicon nitride film selective etching solution is a silicon nitride film selective etching solution of the present invention, a silicon oxide film and a silicon nitride film. It provides a method of etching the formed substrate.
  • Another aspect of the present invention provides a method for manufacturing a semiconductor device, including an etching process performed using the silicon nitride film selective etching solution of the present invention.
  • composition for etching according to the present invention has a feature of high etching selectivity of the nitride film to silicon oxide film, so that the silicon nitride film can be selectively removed and the etching rate of the silicon oxide film can be minimized, and foreign substances that adversely affect semiconductor device properties Problems such as occurrence can be solved.
  • the ability to suppress the etching of the silicon oxide film is maximized, so that a high selectivity ratio of the silicon nitride film to the silicon oxide film can be realized.
  • the silicon-based compound in the form of an alkyl silane triol exhibits a high silicon oxide film etch inhibiting effect even with a small amount added, and thus it is easy to manufacture an etchant for realizing a high selectivity.
  • a high selectivity etchant for semiconductors includes an inorganic acid; Silane-based regulators; And Sulfur-based adjuvants.
  • the performance of passivation of the silicon oxide film of the silane-based regulator is maximized, and through this, the selectivity between the silicon nitride film and the oxide film can be realized up to 2000: 1 or more, and the amount of the silane-based regulator, the selectivity controlling agent, is added. Can be reduced to 1% or less.
  • the high selectivity etchant for semiconductors according to an embodiment of the present invention is silicon particles only by adding a silane-based compound and a sulfur-based auxiliary agent without adding a silicate compound, which has been a problem in the related art. , It is possible to improve the suppression of abnormal growth.
  • the silane-based modulator may be one containing an alkyl group or an amino group having 1 to 3 carbon atoms.
  • the silane-based modulator may be one comprising an alkyl group, an alkoxy group, or an amino group.
  • the silane-based modulator may be a main modulator that controls the etch selectivity of the nitride layer to the silicon oxide layer.
  • the silane-based modifier may be mixed with an inorganic acid to effectively etch the nitride film, and exhibit excellent performance in contact surface roughness and the like.
  • the amino group is not particularly limited as long as it contains an amino group, and may include both an alkyl group and an amino group, such as an amino ethyl group, an amino propyl group, and the like.
  • the silane-based regulator may be one containing one to three alkyl groups.
  • the alkyl group of the silane-based modulator is not particularly limited, and may be, for example, a methyl group, an ethyl group, or a propyl group.
  • the silane-based modulator may include 1 to 6 alkoxy groups, and the alkoxy group may be a methoxy group or an ethoxy group.
  • the selectivity increase rate can be significantly increased by using only the silane-based modulator.
  • the alkoxy group is an alkyl group bonded through an oxygen link (-O-), functions as an electron donor that provides electrons in the etchant, and further includes an alkyl group or an amino group,
  • the role of the electron donor can be further improved.
  • the selectivity when used in combination with an auxiliary or auxiliary additive, the selectivity can be increased more than the silane-based modulator alone, particularly the present invention
  • the sulfur When used with a supplement, the effect can be maximized.
  • the silane-based modulator 3-Aminopropyl (diethoxy) methylsilane, 3- (2-aminoethylamino) propyl triethoxysilane (3- (2 -Aminoethylamino)propyldimethoxymethylsilane, 3-Aminopropyldimethoxymethylsilane, Diethoxydimethylsilane, Diethoxydiphenylsilane, (3-aminopropyl)triethoxysilane ((3 -Aminopropyl)triethoxysilane), (3-glycidyloxypropyl)trimethoxysilane, (Vinyltrimethoxysilane), N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane (N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane), 3-Aminopropyltrimethoxys
  • the silane-based modulator may serve to control an initial selectivity ratio of a nitride film to a silicon oxide film by controlling an etching rate of the silicon oxide film.
  • the content of the silane-based regulator in the high selectivity etchant for semiconductors may be from 0.01% to 1% by weight.
  • the silicon oxide film is over-etched, resulting in a thinner oxide layer or shape deformation, which may deteriorate the quality of the post-process and final products.
  • Capacity capacity
  • the breakdown voltage is lowered
  • a problem of reaching a limit may occur, and when the content of the silane-based modulator exceeds 1% by weight, in the etching solution, sulfur (Sulfur)
  • the effect of increasing the selectivity is insufficient due to the excessive addition of a silane-based regulator, or the ratio of the inorganic acid and water is relatively low, thereby reducing the ability to etch the silicon nitride film, the etching rate of the oxide film is reduced to less than an appropriate value, and the oxide film
  • the deposition phenomenon, not etching may occur, and abnormal growth may occur in the silicon oxide layer.
  • the sulfur (Sulfur)-based adjuvant sulfate (Sulfate), hydrogen sulfate (HydrogenSulfate), peroxide (Persulfate), sulfite (Sulfite), bisulfite (bisulfite), hyposulfate (Hyposulfite), hydro Sulfur containing at least one salt selected from the group consisting of hydrosulfite, metabisulfite, thiosulfate, sulfur dioxide, sulfur trioxide and sulfuric acid Sulfur).
  • the etch rate can be controlled by maximizing the passivation performance of the silicon oxide film of the silane-based modulator, and the selectivity between the silicon nitride film and the oxide film can be realized up to 2000:1 or higher, and the selectivity modifier silane
  • the amount of the series modifier added can be reduced to 1% or less.
  • the sulfur-based adjuvant may be a persulfate-based adjuvant
  • the persulfate-based adjuvant may include a functional group represented by Formula 1 below.
  • the sulfur (Sulfur)-based adjuvant when used alone and mixed with the inorganic acid, there is no effect of controlling the selectivity, but when used with the silane-based modulator may bring about an effect of improving the selectivity.
  • the sulfur-based auxiliary agent when used with a large change in selectivity when using the silane-based modulator alone, can maximize its effect, especially 0 to 2 alkoxy groups of the silane-based modulator When included, the rate of increase in selectivity may be improved when used with a persulfate-based adjuvant.
  • the Sulfur-based adjuvant Ammonium sulfate, Ammonium bisulfite, Ammonium hydrosulfide, Ammonium metabisulfite, Ammonium Sulfite ) And ammonium persulfate (Ammonium persulfate).
  • the content of the sulfur-based auxiliary agent may be 0.05 to 5% by weight.
  • the addition of the control auxiliary agent is insignificant, and the silicon oxide film is over-etched, so that the thickness of the oxide layer may become thin or cause shape deformation. Accordingly, it affects the post-process and the final product, and also increases the capacity applied to the oxide layer, lowers the breakdown voltage, and may reach the limit.
  • the ratio of the silane-based control agent to the content of the sulfur-based auxiliary agent is exceeded, so the effect of increasing the selectivity may be insignificant.
  • the content of the sulfur-based auxiliary agent exceeds 5% by weight, it may not have any effect on the increase in the selectivity, and the etching rate of the oxide film is greatly reduced to less than an appropriate value. The deposition phenomenon may occur rather than the etching of.
  • the inorganic acid may include at least one selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphorous acid, metaphosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, nitric acid and nitrous acid.
  • the inorganic acid may be preferably phosphoric acid, and the phosphoric acid may be used in combination with water or deionized water (DIW).
  • DIW deionized water
  • the phosphoric acid as a strong acid, may be difficult to handle due to its corrosiveness when used alone, but when a small amount of deionized water is mixed and a silane-based modifier is used together, silicon particle induction is suppressed and high. It may be suitable for semiconductor manufacturing processes.
  • the phosphoric acid when used as an etchant together with a silane-based modulator, sufficient etch time for removing the nitride film is secured, no additional process is necessary, and effective field oxide height (EFH) adjustment is easy. can do.
  • EHF effective field oxide height
  • the deionized water preferably 8 to 15% by weight may be included.
  • the content of the inorganic acid in the high selectivity etchant for semiconductors may be 85 to 90% by weight.
  • the effect of etching may be negligible, and when it exceeds 90% by weight, due to the excessive addition of strong acid, the oxide film may be overetched and silicon particles may be caused.
  • the silicon concentration in the high selectivity etchant for semiconductors according to Equation 1 below may be 50 ppm to 1500 ppm.
  • the etch selectivity of the silicon nitride film to the silicon oxide film may be 80:1 to 8000:1.
  • the measurement of the etch selectivity of the silicon nitride film to silicon oxide film is 160
  • the etching time may be measured as a silicon nitride film 5 minutes / silicon oxide film 1 hour.
  • the nitride film when the etch selectivity of the silicon nitride film to silicon oxide film is less than 80:1, the nitride film may not be sufficiently etched to deteriorate reliability and pattern formation, and when it exceeds 8000:1, the nitride film compared to the oxide film This can be over-etched.
  • An etching method of a substrate on which a silicon oxide film and a silicon nitride film is formed according to an embodiment of the present invention includes forming a silicon oxide film and a silicon nitride film on a substrate; And etching the substrate on which the silicon oxide film and the silicon nitride film are formed using a high selectivity etchant for semiconductors, wherein the high selectivity etchant for semiconductors is high selectivity for semiconductors according to an embodiment of the present invention. It is a non-etching liquid.
  • the etching of the substrate on which the silicon oxide film and the silicon nitride film is formed is 160
  • the silicon nitride film is etched for 5 minutes
  • the oxide film is etched for 1 hour
  • the etching rate may be calculated by dividing the thickness difference before and after etching of each film by the etching time in minutes.
  • an inorganic acid A silicon-based compound represented by Formula 2 below; And water; to provide a silicon nitride film selective etching solution.
  • L is a single bond, alkylene having 1 to 10 carbons or cycloalkylene having 4 to 8 carbons, R 1 is hydrogen, hydroxy, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, and R 2 is hydrating Roxy, an alcohol having 1 to 10 carbons or alkoxy having 1 to 10 carbons, and n is an integer of 1 to 10.
  • L when n is an integer of 2 or more, L may be the same or different, respectively.
  • R 1 when n is an integer of 2 or more, R 1 may be the same or different, respectively.
  • the silicon-based compound represented by Chemical Formula 2 may be prepared by synthesizing an alkoxy-based silane and a sulfur or peroxide-based material.
  • the silicon nitride film selective etchant of the present invention may include a silicon-based compound represented by Chemical Formula 2 as a selectivity ratio main modulator to maximize passivation performance of the silicon oxide film.
  • the silicon-based compound represented by Chemical Formula 2 can realize a high selectivity ratio of the silicon nitride film to the silicon oxide film with only a small amount added, reducing the addition amount of the selectivity modifier to 1 wt%, preferably 0.1 wt% or less
  • the etch rate of the silicon oxide film can be freely controlled by adjusting the addition amount.
  • L is alkylene having 1 to 10 carbons or cycloalkylene having 4 to 8 carbons
  • R 1 is hydrogen, hydroxy or alkyl having 1 to 6 carbons
  • R 2 is Hydroxy, alcohol having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms
  • n may be an integer of 1 to 5.
  • L is alkylene having 1 to 5 carbons
  • R 1 is hydrogen or alkyl having 1 to 5 carbons
  • R 2 is hydroxy
  • n is an integer of 1 to 3 Can be.
  • the silicon-based compound represented by Chemical Formula 2 is 3-(trihydroxysilyl)propyl sulfamic acid, methyl (3-(trihydroxysilyl)propyl) sulfamic acid, 3-(3 -(Trihydroxysilyl)propylamino)propylsulfamic acid, 3-(3-(trihydroxysilyl)propylamino)propylsulfamic acid, 3-(3-(3-(trihydroxysilyl)propylamino )Propylamino)propylsulfamic acid and any one selected from the group consisting of methyl(3-(methyl(3-(methyl(3-(trihydroxysilyl)propyl)amino)propyl)amino)propyl)sulphamic acid May be
  • the inorganic acid may include at least one selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphorous acid, metaphosphoric acid, polyphosphoric acid, sulfuric acid, sulfurous acid, nitric acid and nitrous acid.
  • the inorganic acid may be preferably phosphoric acid, and the phosphoric acid may be used in combination with water or deionized water (DIW).
  • DIW deionized water
  • the phosphoric acid may be difficult to handle due to corrosiveness when used alone as a strong acid, but when mixed with a small amount of deionized water and added with the compound represented by Chemical Formula 2, silicon particles are used. There is an effect that can suppress the trigger.
  • the content of the inorganic acid may be 85 to 90% by weight.
  • the etching effect may be insignificant, and when it exceeds 90% by weight, the oxide film may be over-etched and silicon particles may be caused by excessive addition of strong acid.
  • the content of the silicon-based compound represented by Chemical Formula 2 in the silicon nitride film selective etching solution may be 0.01 to 3% by weight.
  • the content of the silicon-based compound represented by Chemical Formula 2 may be 0.01% by weight to 1% by weight, more preferably 0.01% by weight to 0.5% by weight, It may be even more preferably from 0.01% to 0.1% by weight.
  • the effect of improving the selectivity may be insignificant, and the thickness of the oxide film layer may be thinned or formed by over-etching the silicon oxide film. Deformation may be caused, thereby deteriorating the quality of the post-process and the final product, and the capacity of the oxide layer may be increased and a breakdown voltage may be lowered to reach a limit.
  • the silicon nitride film selective etching solution when the content of the silicon-based compound represented by Chemical Formula 2 exceeds 3% by weight, the ratio of inorganic acid and water may be relatively low, so that the silicon nitride film etching ability may be reduced, and etching of the oxide film As the speed decreases below an appropriate value and deposition phenomenon occurs, not etching of the oxide film, abnormal growth may occur in the silicon oxide film portion.
  • the inorganic acid is 85% by weight to 90% by weight
  • the silicon-based compound represented by the formula (2) is 0.01% by weight to 3% by weight, it may be to include a residual amount of water.
  • the selective etching solution of the silicon nitride film may have a selection ratio of a silicon nitride film to a silicon oxide film of 100:1 or more.
  • the silicon nitride film selective etching solution, the silicon nitride film to silicon oxide film selection ratio, 100: 1 to : May be one person.
  • the silicon nitride film selective etching solution when the selection ratio of the silicon nitride film to the silicon oxide film is less than 100:1, the silicon nitride film is not sufficiently etched during the semiconductor manufacturing process, so reliability may be reduced and pattern formation may be difficult.
  • the measurement of the etch selectivity of the silicon nitride film to silicon oxide film is 160
  • the etching time may be measured as a silicon nitride film 5 minutes, a silicon oxide film 1 hour.
  • the silicon nitride film selective etching solution the etching rate for the silicon nitride film is 400 to 500 Is, the etching rate for the silicon oxide film is 3 It may be the following.
  • the measurement of the silicon etch rate is 160
  • the silicon nitride film may be measured by etching for 5 minutes and the silicon oxide film for 1 hour.
  • the silicon nitride film selective etching solution may be to suppress particle generation during the etching process.
  • the silicon nitride film selective etching solution by suppressing an increase in the concentration of silicon during the etching process, can reduce the occurrence of particles of silicon compounds and the abnormal growth of the oxide film surface, excellent storage stability and etching stability effect There is.
  • Another aspect of the present invention forming a silicon oxide film and a silicon nitride film on a substrate; And etching the substrate on which the silicon oxide film and the silicon nitride film are formed using a silicon nitride film selective etching solution, wherein the silicon nitride film selective etching solution is a silicon nitride film selective etching solution according to any one of claims 1 to 11 It provides a method for etching a substrate on which a silicon oxide film and a silicon nitride film are formed.
  • Another aspect of the present invention provides a method of manufacturing a semiconductor device, including an etching process performed using the silicon nitride film selective etching solution of any one of claims 1 to 11.
  • the silane-based modifier is concentrated and dissolved in an inorganic acid (phosphoric acid), and a sulfur-based auxiliary agent is concentrated and dissolved in another inorganic acid (phosphoric acid).
  • phosphoric acid another inorganic acid
  • Triethoxymethylsilane Triethoxyethylsilane, 3-Aminopropyl Triethoxysilane, 3-Aminopropyl(diethoxy)methylsilane or Bis[3-(trimethoxysilyl)propyl]amine was used,
  • Ammonium sulfate As the added sulfur-based adjuvant, Ammonium sulfate, Ammonium bisulfite, Ammonium hydrosulfite, Ammonium metabisulfite, Ammonium Sulfite or Ammonium persulfate was used.
  • amino silane bis(3-triethoxysilyl-propyl)amine (Bis(3-triethoxysilyl-propyl) amine), bis(3-trimethoxysilyl-propyl)amine (Bis(3-trimethoxysilyl- propyl) amine), 3-aminopropyl-methyldiethoxysilane, 3-aminopropyltri-ethoxysilane, 3-aminopropyltri-methoxysilane (3 -aminopropyltri-methoxysilane, triamino-functional propyltrimethoxy-silane, diethylaminomethyltriethoxysilane, 3-ureidopropyltriethoxysilane ), aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, tetra(methylethylketoxime)silane (T)
  • ammonium persulfate ammonium persulfide compound
  • ammonium bisulfite ammonium sulfite
  • ammonium hydrosulfite ammonium metabisulfite
  • ammonium metabisulfite ammonium persulfate
  • Silicon by using a mixed or silane-based modifier alone by varying the type or content of a silane-based modulator in a high selectivity etchant solution for semiconductors prepared according to Preparation Example 1, and by varying the type or capacity of a sulfur-based auxiliary agent. Concentration was measured.
  • the etching rate for the silicon nitride film and the etching rate for the silicon oxide film were respectively measured using the high selectivity etchant solution for semiconductors prepared according to Preparation Example 1, and then the selectivity was calculated.
  • the etch of each membrane is 163
  • the silicon nitride film was etched for 5 minutes and the oxide film was etched for 1 hour.
  • the etch rate was calculated by dividing the thickness difference before and after the etch of each membrane by the etch time in minutes.
  • Reflectometer (Filmetrics F20) was used to measure the film thickness.
  • APTES 3-aminopropyltriethoxysilane
  • TAMS 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane
  • silicon nitride film etchant was prepared in the same manner as in Example 1.
  • the etch rate for the silicon nitride film and the etch rate for the silicon oxide film were measured, respectively, and the selectivity was calculated.
  • the etch of each membrane is 160
  • the silicon nitride film was etched for 5 minutes and the oxide film was etched for 1 hour.
  • the etch rate was calculated by dividing the thickness difference before and after the etch of each membrane by the etch time in minutes. Reflectometer (Filmetrics F20) was used to measure film thickness.
  • the high selectivity of the silicon nitride film to the silicon oxide film can be realized in the etchant of the embodiment.

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Abstract

La présente invention concerne un agent de gravure hautement sélectif pour un semi-conducteur et, plus particulièrement, un agent de gravure hautement sélectif pour un semi-conducteur, comprenant : un acide inorganique ; un modificateur à base de silane ; et un auxiliaire à base de soufre. De plus, la présente invention concerne un agent de gravure sélectif pour un film de nitrure de silicium et un procédé de fabrication d'un dispositif à semi-conducteur faisant appel à celui-ci, et un aspect de la présente invention concerne un agent de gravure sélectif pour un film de nitrure de silicium, comprenant : un acide inorganique ; un composé à base de silicium ; et de l'eau.
PCT/KR2019/016069 2018-12-11 2019-11-22 Agent de gravure hautement sélectif pour semi-conducteur, agent de gravure sélectif pour film de nitrure de silicium et fabrication de dispositif à semi-conducteur faisant appel à ceux-ci WO2020122454A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2018-0159424 2018-12-11
KR20180159424 2018-12-11
KR1020190060753A KR102307189B1 (ko) 2018-12-11 2019-05-23 반도체용 고선택비 식각액
KR10-2019-0060753 2019-05-23
KR10-2019-0092999 2019-07-31
KR1020190092999A KR102278765B1 (ko) 2019-07-31 2019-07-31 실리콘 질화막 선택적 식각액 및 이를 이용한 반도체 소자의 제조 방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000058500A (ja) * 1998-08-07 2000-02-25 Matsushita Electron Corp エッチング液，その製造方法及びエッチング方法
US20050159011A1 (en) * 2004-01-21 2005-07-21 Thirumala Vani K. Selective etching silicon nitride
KR20110037741A (ko) * 2009-10-07 2011-04-13 테크노세미켐 주식회사 실리콘질화막에 대한 고선택비 식각용 조성물
KR20170066180A (ko) * 2015-12-04 2017-06-14 솔브레인 주식회사 식각용 조성물 및 이를 이용한 반도체 소자의 제조방법
KR20170093430A (ko) * 2016-02-05 2017-08-16 동우 화인켐 주식회사 실리콘 질화막 식각액 조성물 및 이를 이용하는 반도체 소자 및 tft 어레이 기판의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000058500A (ja) * 1998-08-07 2000-02-25 Matsushita Electron Corp エッチング液，その製造方法及びエッチング方法
US20050159011A1 (en) * 2004-01-21 2005-07-21 Thirumala Vani K. Selective etching silicon nitride
KR20110037741A (ko) * 2009-10-07 2011-04-13 테크노세미켐 주식회사 실리콘질화막에 대한 고선택비 식각용 조성물
KR20170066180A (ko) * 2015-12-04 2017-06-14 솔브레인 주식회사 식각용 조성물 및 이를 이용한 반도체 소자의 제조방법
KR20170093430A (ko) * 2016-02-05 2017-08-16 동우 화인켐 주식회사 실리콘 질화막 식각액 조성물 및 이를 이용하는 반도체 소자 및 tft 어레이 기판의 제조방법

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