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WO2013069499A1 - Procédé de traitement d'une surface de tranche et liquide de traitement de surface, agent de traitement de surface et liquide de traitement de surface, procédé de traitement de surface pour des tranches contenant du nitrure de silicium - Google Patents

Procédé de traitement d'une surface de tranche et liquide de traitement de surface, agent de traitement de surface et liquide de traitement de surface, procédé de traitement de surface pour des tranches contenant du nitrure de silicium Download PDF

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Publication number
WO2013069499A1
WO2013069499A1 PCT/JP2012/077950 JP2012077950W WO2013069499A1 WO 2013069499 A1 WO2013069499 A1 WO 2013069499A1 JP 2012077950 W JP2012077950 W JP 2012077950W WO 2013069499 A1 WO2013069499 A1 WO 2013069499A1
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WIPO (PCT)
Prior art keywords
wafer
silicon
surface treatment
silicon nitride
sin
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PCT/JP2012/077950
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English (en)
Japanese (ja)
Inventor
真規 斎藤
忍 荒田
崇 齋尾
公文　創一
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Central Glass Co Ltd
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Central Glass Co Ltd
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Publication date
Priority claimed from JP2011247497A external-priority patent/JP5953707B2/ja
Priority claimed from JP2011247502A external-priority patent/JP2013104954A/ja
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to KR1020147013734A priority Critical patent/KR101680438B1/ko
Publication of WO2013069499A1 publication Critical patent/WO2013069499A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • 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
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz

Definitions

  • the present invention relates to a silicon element-containing wafer surface treatment method for improving the adhesion between a resist and a silicon element-containing wafer in semiconductor device production and the like, and a silicon element-containing wafer surface treatment solution. Furthermore, the present invention relates to a surface treatment agent for the wafer, a surface treatment liquid, and a method for treating the surface of the wafer, which improve the adhesion between a wafer containing a resist and silicon nitride in semiconductor device manufacturing or the like.
  • a fine resist pattern is formed on the surface of the silicon wafer through lithography and etching. Further, the wafer surface is etched using this resist pattern as a mold, and an uneven pattern is formed on the wafer surface.
  • the wafer surface can be hydrophobized using a silane coupling agent such as HMDS before film formation of the resist. It is known that adhesion can be improved (for example, Patent Document 1). After this treatment, a resist film is formed, whereby the adhesion between the wafer and the resist is improved, and a good resist pattern can be formed.
  • a silane coupling agent such as a method of immersing a wafer in a treatment liquid containing a silane coupling agent or a method of spinning a treatment liquid containing a silane coupling agent on the wafer is used.
  • a method of bringing a processing solution into contact with a wafer or a method of spraying a gas obtained by bubbling a silane coupling agent with a gas such as nitrogen onto the heated wafer surface (vapor prime method) is known (for example, Patent Document 1).
  • vapor prime method for example, Patent Document 1
  • Patent Documents 2 and 3 in view of the processing performance of the silane coupling agent.
  • Adhesion between a wafer containing silicon element (hereinafter sometimes referred to as “silicon element-containing wafer” or simply “wafer”) and the resist can be improved by sufficiently hydrophobizing the wafer surface.
  • silicon element-containing wafer hereinafter sometimes referred to as “silicon element-containing wafer” or simply “wafer”
  • the wafer is hydrophobized by a method (vapor prime method) in which a gas obtained by bubbling a silane coupling agent with a gas such as nitrogen is sprayed onto the heated wafer surface.
  • the present invention can increase the adhesion between the wafer and the resist by hydrophobizing the surface of the wafer containing silicon element, which does not require a special apparatus, has low energy loss, and has improved throughput. It is an object to provide a surface treatment method for a silicon element-containing wafer and a surface treatment liquid for a silicon element-containing wafer (hereinafter, sometimes referred to as “surface treatment liquid” or simply “treatment liquid”). . ⁇ From the second perspective>
  • the adhesion between the wafer and the resist can be improved by sufficiently hydrophobizing the wafer surface.
  • a reactive site such as a hydroxyl group present on the wafer surface to a hydrophobic compound.
  • silicon nitride-containing wafer hereinafter referred to as “silicon nitride-containing wafer”, “silicon nitride wafer”, or simply “wafer”
  • since there are few hydroxyl groups on the wafer surface In some cases, it is difficult to impart sufficient hydrophobicity to the wafer surface, and the adhesion between the wafer and the resist cannot be improved.
  • the present invention is a surface treatment agent for silicon nitride-containing wafers (hereinafter referred to as “surface treatment agent”, or simply, which can improve the adhesion between the wafer and the resist by hydrophobizing the silicon nitride-containing wafer surface.
  • surface treatment agent silicon nitride-containing wafer surface treatment liquid
  • treatment liquid silicon nitride-containing wafer surface treatment liquid
  • the present invention is a method for treating a surface of a wafer, which improves the adhesion between the wafer and a resist by hydrophobizing the wafer surface containing silicon element, the following steps: A surface treatment step of bringing the wafer surface into contact with a surface treatment solution for a silicon element-containing wafer to hydrophobize the wafer surface; A treatment liquid removal step of removing the treatment liquid from the wafer surface; For a silicon element-containing wafer including a resist film forming step for forming a resist film on the wafer surface, and including a silicon compound represented by the following general formula [I-1], an acid, and a diluting solvent in the surface treatment step A surface treatment method for a silicon element-containing wafer, wherein a surface treatment liquid is used.
  • each R 1 is independently a hydrogen group or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group is substituted with a halogen atom. May be.
  • X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and a is an integer of 1 to 3.
  • the surface treatment step is a spin treatment of the silicon element-containing wafer with the treatment liquid or an immersion treatment of the silicon element-containing wafer in the treatment liquid.
  • the present invention also provides a silicon element-containing wafer surface treatment solution used in the above-described silicon element-containing wafer surface treatment method, the silicon compound represented by the following general formula [I-1], an acid, and a diluting solvent:
  • R 1 a SiX 4-a [I-1] each R 1 is independently a hydrogen group or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group is substituted with a halogen atom. May be.
  • X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and a is an integer of 1 to 3. ]
  • the silicon compound is preferably a silicon compound represented by the following general formula [I-2].
  • R 1 3 SiX [I-2] [In the formula [I-2], R 1 and X are the same as in the general formula [I-1]. ]
  • the silicon compound is preferably a silicon compound represented by the following general formula [I-3].
  • R 2 (CH 3 ) 2 SiX [I-3] [In the formula [I-3], R 2 is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • X is the same as in general formula [I-1]. ]
  • R 2 preferably has 6 to 18 carbon atoms.
  • the acid contained in the silicon element-containing wafer surface treatment liquid is preferably an organic acid.
  • the silicon compound is preferably contained in an amount of 0.1 to 50% by mass with respect to 100% by mass of the total amount of the surface treatment liquid for silicon element-containing wafer.
  • the present invention provides a silicon nitride-containing surface treatment agent for a wafer for improving adhesion between the wafer and the resist by hydrophobizing the wafer surface before forming a resist film on the wafer surface containing silicon nitride.
  • the total number of carbon atoms contained as R 1 is 6 or more.
  • X is independently of each other at least one selected from a monovalent functional group in which the element bonded to the silicon element is nitrogen, a monovalent functional group in which the element bonded to the silicon element is oxygen, and a halogen group
  • a is an integer of 1 to 3.
  • the silicon compound is preferably a silicon compound represented by the following general formula [II-2].
  • R 1 3 SiX [II-2] [In the formula [II-2], R 1 and X are the same as in the general formula [II-1]. ]
  • the silicon compound is preferably a silicon compound represented by the following general formula [II-3].
  • R 2 (CH 3 ) 2 SiX [II-3] [In the formula [II-3], R 2 is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • X is the same as in the general formula [II-1]. ]
  • the silicon compound is preferably a silicon compound represented by the following general formula [II-4].
  • R 3 (CH 3 ) 2 SiY [II-4] [In the formula [II-4], R 3 is a hydrocarbon group having 4 to 18 carbon atoms in which at least a part of hydrogen atoms are substituted with halogen atoms, and Y is a halogen group. ]
  • a silicon nitride-containing surface treatment solution for a wafer obtained by dissolving the silicon nitride-containing wafer surface treatment agent with a diluent solvent, wherein the silicon compound is contained with respect to 100% by mass of the treatment solution.
  • a silicon nitride-containing surface treatment liquid for a wafer characterized by containing 0.1 to 50% by mass.
  • a silicon nitride-containing wafer surface treatment liquid obtained by dissolving the silicon nitride-containing wafer surface treatment agent and acid with a diluting solvent, wherein the silicon is added to the total amount of the treatment liquid of 100% by mass.
  • the silicon compound is preferably a silicon compound represented by the following general formula [II-5].
  • R 4 (CH 3 ) 2 SiZ [II-5] [In the formula [II-5], R 4 is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • Z is a monovalent functional group in which the element bonded to the silicon element is nitrogen, or a monovalent functional group in which the element bonded to the silicon element is oxygen. ]
  • R 4 preferably has 6 to 18 carbon atoms.
  • Z in the general formula [II-5] is preferably a monovalent functional group in which the element bonded to the silicon element is nitrogen.
  • the wafer surface treatment method for improving the adhesion between the wafer and the resist by hydrophobizing the wafer surface containing silicon nitride comprising the following steps: Contact the wafer surface with a silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer surface treatment solution, or contact the wafer surface with a silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer surface treatment solution.
  • a surface treatment step for hydrophobizing the wafer surface A resist film forming step for forming a resist film on the wafer surface, wherein the silicon nitride-containing wafer surface treatment agent or the silicon nitride-containing wafer surface treatment solution described above is used in the surface treatment step.
  • a surface treatment method for a silicon nitride-containing wafer comprising the following steps: Contact the wafer surface with a silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer surface treatment solution, or contact
  • a surface treatment solution for silicon nitride-containing wafer is brought into contact with the wafer surface to make the wafer surface hydrophobic.
  • the surface treatment agent for a silicon nitride-containing wafer of the present invention a surface treatment liquid, and the surface treatment method of the wafer, it is possible to impart good hydrophobicity to the wafer surface containing silicon nitride. Accordingly, the silicon nitride-containing wafer hydrophobized by using the surface treatment agent for silicon nitride-containing wafers of the present invention, the surface treatment liquid, and the wafer surface treatment method has good adhesion to the resist. Be expected.
  • a wafer containing a silicon element to be surface-treated using the treatment liquid of the present invention is a silicon wafer, a silicon wafer having a silicon oxide film formed thereon by a thermal oxidation method, a CVD method, a sputtering method, a CVD method, A silicon nitride film or a polysilicon film formed by sputtering or the like, and a silicon oxide film, a polysilicon film, or a silicon wafer surface naturally oxidized are also included.
  • a wafer composed of a plurality of components containing silicon and / or silicon oxide, a silicon carbide wafer, and a wafer in which various films containing a silicon element are formed on the wafer can be used as the wafer.
  • various films containing silicon elements may be formed on a wafer not containing silicon elements, such as sapphire wafers, various compound semiconductor wafers, and plastic wafers.
  • the treatment liquid hydrophobizes the wafer surface containing silicon element, the film surface containing silicon element formed on the wafer, and the wafer or the wafer formed with the pattern containing silicon element formed from the film. can do.
  • the cleaning solution used for the cleaning include water, an organic solvent, a mixed solution of water and an organic solvent, and a solution in which an acid or a base is dissolved.
  • the silicon element-containing wafer may be immersed in the cleaning liquid, or the wafer is cleaned one by one by supplying the cleaning liquid to the vicinity of the rotation center while rotating the silicon element-containing wafer substantially horizontally. Spin processing may be performed. Further, the cleaning liquid may be used in a heated state.
  • the present invention is a method for treating a surface of a wafer, which improves the adhesion between the wafer and a resist by hydrophobizing the wafer surface containing silicon element, the following steps: A surface treatment step of bringing the wafer surface into contact with a surface treatment solution for a silicon element-containing wafer to hydrophobize the wafer surface; A treatment liquid removal step of removing the treatment liquid from the wafer surface; For a silicon element-containing wafer including a resist film forming step for forming a resist film on the wafer surface, and including a silicon compound represented by the general formula [I-1], an acid, and a diluting solvent in the surface treatment step A surface treatment method for a silicon element-containing wafer, wherein a surface treatment liquid is used.
  • a silicon element-containing surface treatment solution for wafer is brought into contact with the wafer surface to make the wafer surface hydrophobic.
  • a method of bringing the surface treatment liquid for the silicon element-containing wafer into contact with the wafer surface is not limited, but the silicon element-containing wafer is spin-treated with the treatment liquid, or the silicon element-containing wafer is immersed in the treatment liquid Is preferred.
  • the spin processing is, for example, a method of processing wafers one by one by supplying liquid to the vicinity of the rotation center while rotating while holding the wafer substantially horizontal.
  • the immersion treatment is, for example, a method in which a plurality of wafers are immersed in a silicon element-containing wafer surface treatment solution immersion bath at a time. Since the surface treatment liquid for silicon element-containing wafers of the present invention can impart sufficient hydrophobicity to the wafer surface in a short period of time even in the surface treatment method in which the liquid and the wafer are brought into contact with each other, as described above It can also be applied to spin processing and immersion processing. In addition, when the said spin process is performed using the surface treatment liquid for silicon element containing wafers of this invention, since it can perform continuously from a surface treatment process to a resist film-forming process, it is thought that it leads to simplification of a production process.
  • the hydrophobicity imparted to the wafer surface by the surface treatment method using the silicon element-containing wafer surface treatment liquid of the present invention does not necessarily have to be imparted continuously, and is not necessarily imparted uniformly. Although not necessary, in order to further improve the adhesiveness with the resist, it is more preferable that it is applied continuously and uniformly.
  • the treatment liquid may be maintained at 10 to 160 ° C. A temperature of 15 to 120 ° C. is particularly preferable.
  • the surface treatment liquid for the silicon element-containing wafer is removed from the hydrophobicized wafer surface.
  • the method of removing may be a method of removing the processing liquid by drying it from the wafer surface, or after replacing the processing liquid on the wafer surface with a solvent or water different from the processing liquid, A method of removing water by drying may also be used.
  • a known drying method such as a spin drying method, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, or vacuum drying can be applied.
  • the solvent or water is replaced with an uncured resist used in the resist film forming process of the next process, whereby a surface treatment process or a treatment liquid removal process is performed.
  • the resist film forming step may be performed continuously.
  • the surface treatment process is performed by a spin process, and the subsequent treatment liquid removal process and the resist film formation process are also performed by the same spin process, the surface treatment process to the resist film formation process are continuously performed as described above. Therefore, improvement in throughput can be expected.
  • a resist film forming step for forming a resist film on the hydrophobic surface of the wafer is performed.
  • the method for forming the resist is not particularly limited, and a known method can be used.
  • a spin film formation process in which a resist before curing is supplied to the vicinity of the rotation center while rotating the wafer while holding the wafer substantially horizontal to form a resist on the wafer surface one by one, is more preferably used. .
  • a pattern is formed on the wafer surface through the following operations. That is, after performing the resist film forming step, a pattern is formed on the resist, and then a pattern is formed on the wafer surface.
  • the method is not particularly limited as long as a pattern is formed, but as a general method, after applying a resist to the wafer surface in a resist film forming step, the resist is exposed through a resist mask and exposed. A resist having a desired pattern is produced by etching away the resist or the resist that has not been exposed. A resist having a pattern can also be obtained by pressing a mold having a pattern against the resist. Subsequently, the wafer is etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is removed, a silicon wafer having a pattern is obtained.
  • the present invention also provides a silicon element-containing wafer surface treatment liquid used in the above-described silicon element-containing wafer surface treatment method, the silicon compound represented by the general formula [I-1], an acid, and a diluting solvent.
  • the hydrocarbon group represented by R 1 of the silicon compound represented by the general formula [I-1] is a hydrophobic group, and makes the wafer surface after the treatment a good hydrophobic surface.
  • the hydrophobic group can express hydrophobicity not only on the surface of silicon oxide or the like having a large number of hydroxyl groups per unit area but also on the surface of silicon nitride or the like having a small number of hydroxyl groups per unit area.
  • the group represented by X which is the reactive site is a functional group for reacting with a hydroxyl group present on the wafer surface and forming a siloxane bond with the silicon element on the wafer surface.
  • the above-mentioned silicon compound and wafer surface can be contacted in a short time. It is possible to chemically react with a hydroxyl group, and to impart hydrophobicity to the wafer surface.
  • Examples of the silicon compound represented by the general formula [I-1] include (CH 3 ) 3 SiNH 2 , C 2 H 5 (CH 3 ) 2 SiNH 2 , C 3 H 7 (CH 3 ) 2 SiNH 2 , C 4 H 9 (CH 3 ) 2 SiNH 2 , C 5 H 11 (CH 3 ) 2 SiNH 2 , C 6 H 13 (CH 3 ) 2 SiNH 2 , C 7 H 15 (CH 3 ) 2 SiNH 2 , C 8 H 17 (CH 3 ) 2 SiNH 2 , C 9 H 19 (CH 3 ) 2 SiNH 2 , C 10 H 21 (CH 3 ) 2 SiNH 2 , C 11 H 23 (CH 3 ) 2 SiNH 2 , C 12 H 25 ( CH 3 ) 2 SiNH 2 , C 13 H 27 (CH 3 ) 2 SiNH 2 , C 14 H 29 (CH 3 ) 2 SiNH 2 , C 15 H 31 (CH 3 ) 2 SiNH 2 , C 16 H 33 (CH 3 ) 2 SiNH 2, C 17 H 35 (
  • the halogen atom to be substituted is preferably a fluorine atom in consideration of the hydrophobizing performance.
  • the monovalent functional group represented by X in the general formula [I-1] whose element bonded to the silicon element is nitrogen is carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium. , Fluorine, chlorine, bromine, iodine, or any other functional group, for example, —NHSi (CH 3 ) 3 group, —NHSi (CH 3 ) 2 C 4 H 9 group, —NHSi (CH 3 ) 2 C 8 H 17 group, —N (CH 3 ) 2 group, —N (C 2 H 5 ) 2 group, —N (C 3 H 7 ) 2 group, —N (CH 3 ) (C 2 H 5 ) group, —NH (C 2 H 5 ) group, —NCO group, imidazole group, acetamide group and the like.
  • a in the general formula [I-1] may be an integer of 1 to 3, but when a is 1 or 2, when the treatment solution is stored for a long period of time, polymerization of the silicon compound may occur due to water contamination. May occur, and insoluble matter may be deposited in the treatment liquid, or the hydrophobicity-imparting effect of the treatment liquid may be reduced, so that the storage period may be shortened. Therefore, in consideration of the pot life of the treatment liquid, those in which a in formula [I-1] is 3 (that is, the silicon compound represented by formula [I-2]) are preferable.
  • R 1 is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms or a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom
  • a compound composed of two methyl groups that is, a silicon compound represented by the above general formula [I-3]
  • a compound composed of two methyl groups is preferable because of its high reaction rate with hydroxyl groups on the wafer surface. This is because the steric hindrance due to the hydrophobic group has a great influence on the reaction rate in the reaction between the hydroxyl group on the wafer surface and the silicon compound, and the alkyl chain bonded to the silicon element has the remaining two except the longest one. This is because a shorter one is preferable.
  • a silicon compound having the structure as described above there is a tendency that excellent hydrophobicity can be imparted to the wafer surface, and the number of hydroxyl groups per unit area is small. Since hydrophobicity can be provided, it is preferable.
  • the carbon number of R 2 in the general formula [I-3] is 6 to 18 because the effect of imparting hydrophobicity to the wafer surface is great. It is preferable to use the treatment liquid as described above because it is easy to impart more excellent hydrophobicity to the surface of the surface such as silicon nitride having a small number of reactive sites on the surface.
  • the silicon compound is preferably contained in an amount of 0.1 to 50% by mass with respect to the total amount of the treatment liquid of the present invention of 100% by mass, and more preferably 0 to the total amount of the treatment liquid of 100% by mass. .3 to 20% by mass. If the silicon compound is less than 0.1% by mass, it reacts with a small amount of moisture contained in the diluent solvent and is easily deactivated, so the ability to hydrophobize is insufficient and the wafer surface cannot be sufficiently hydrophobized. There is a case. On the other hand, when it is more than 50% by mass, there is a concern that it remains as an impurity on the wafer surface, and it is not preferable from the viewpoint of cost.
  • the treatment liquid of the present invention may contain two or more types of silicon compounds represented by the general formula [I-1], and the silicon compound represented by the general formula [I-1] Silicon compounds other than the silicon compound represented by the general formula [I-1] may be contained.
  • the treatment liquid of the present invention contains an acid.
  • the presence of the acid promotes the reaction between the silicon compound and the hydroxyl group on the wafer surface.
  • examples of such acids include water-free acids such as trifluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, and hydrogen chloride. It is done.
  • acids such as trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride, and the like are preferable.
  • organic acids such as trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride are preferable, and the acid contains moisture.
  • the acid contains moisture.
  • the addition amount of the acid is preferably 0.01 to 100% by mass with respect to 100% by mass of the total amount of the silicon compound. If the amount added is small, the catalytic effect is lowered, which is not preferable. Moreover, even if it adds excessively, a catalyst effect will not improve, but when it increases more than a silicon compound, a catalyst effect may fall conversely. Furthermore, there is a concern that the impurities may remain on the wafer surface as impurities. For this reason, the addition amount of the acid is preferably 0.01 to 100% by mass, more preferably 0.1 to 50% by mass with respect to 100% by mass of the total amount of the silicon compound.
  • the treatment liquid of the present invention contains a diluting solvent.
  • the dilution solvent only needs to dissolve the silicon compound and the acid.
  • hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, lactone solvents, carbonate solvents Organic solvents such as alcohols, polyhydric alcohol derivatives, nitrogen element-containing solvents are preferably used.
  • the reactive site of the silicon compound in the treatment liquid (X in the general formula [I-1]) may be hydrolyzed by water to form a silanol group (Si—OH). There is.
  • silicon compounds may be bonded to each other to form a dimer. Since this dimer has low reactivity with the hydroxyl group on the wafer surface, it may take a long time to hydrophobize the wafer surface, so it is not preferable to use water as a diluting solvent.
  • the silicon compound easily reacts with a protic solvent, it is particularly preferable to use an aprotic solvent as the organic solvent because hydrophobicity is easily developed in a short time.
  • the aprotic solvent is both an aprotic polar solvent and an aprotic apolar solvent.
  • aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, lactone solvents, carbonate solvents, polyhydric alcohol derivatives having no hydroxyl group, N Examples thereof include nitrogen element-containing solvents having no —H bond.
  • hydrocarbons examples include toluene, benzene, xylene, hexane, heptane, and octane.
  • esters examples include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether.
  • examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like
  • ketones examples include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and cyclohexanone.
  • halogen-containing solvent examples include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, 1, 1, 1, 3, 3-pentane.
  • Hydrofluorocarbons such as fluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora H (manufactured by Nippon Zeon Co., Ltd.), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoro Hydrofluoroethers such as fluoroisobutyl ether, Asahiklin AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec7100, Nove7200, Novec7300, and Novec7600 (all from 3M), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, Chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-p
  • Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of the lactone solvents include ⁇ -butyrolactone, ⁇ -valero Lactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ -undecanolactone, ⁇ -dodecanolactone, ⁇ -valerolactone, ⁇ -hexanolactone , ⁇ -octanolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ -undecanolactone, ⁇ -dodecanolactone , ⁇ -hexanolactone, etc.
  • examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, etc.
  • a non-flammable solvent for a part or all of the dilution solvent because the processing liquid becomes non-flammable or the flash point becomes high, and the risk of the processing liquid is reduced.
  • Many of the halogen-containing solvents are nonflammable, and the nonflammable halogen-containing solvent can be suitably used as a nonflammable diluent solvent.
  • GHS International Harmonized System for Classification and Labeling of Chemicals
  • a solvent having a flash point of 93 ° C. or lower is defined as “flammable liquid”. Therefore, even if it is not a nonflammable solvent, if a solvent having a flash point exceeding 93 ° C. is used as the dilution solvent, the flash point of the treatment liquid tends to be 93 ° C. or higher, and the treatment liquid falls under “flammable liquid”. This is preferable from the viewpoint of safety.
  • lactone solvents since many lactone solvents, carbonate solvents and polyhydric alcohol derivatives have a high flash point, it is preferable to use them as solvents since the risk of the treatment liquid can be reduced.
  • the dilution solvent may be present as long as it is a trace amount of water. However, if this water is contained in a large amount in the solvent, the silicon compound may be hydrolyzed by the water and the reactivity may be lowered. For this reason, it is preferable to reduce the amount of water in the solvent, and the amount of water is preferably less than 1 mole in terms of molar ratio to the silicon compound when mixed with the silicon compound. It is particularly preferable to make it less than 5 mole times.
  • the surface treatment agent for a silicon nitride-containing wafer treats the wafer surface before forming a resist film on the wafer surface containing silicon nitride, and adheres the wafer to the resist. It is a silicon nitride-containing surface treatment agent for wafers.
  • the surface treatment agent is a surface treatment agent for hydrophobizing the silicon nitride-containing wafer surface, and the treatment agent is a silicon compound represented by the following general formula [II-1]: This is a silicon nitride-containing surface treatment agent for wafers.
  • R 1 a SiX 4-a [II-1]
  • R 1 are each independently of the other hydrogen group, or a carbon atoms is a hydrocarbon group of 1 to 18, hydrogen atoms of the hydrocarbon group substituted with a halogen atom May be.
  • the total number of carbon atoms contained as R 1 is 6 or more.
  • X is independently of each other at least one selected from a monovalent functional group in which the element bonded to the silicon element is nitrogen, a monovalent functional group in which the element bonded to the silicon element is oxygen, and a halogen group
  • a is an integer of 1 to 3.
  • the hydrocarbon group represented by R 1 is a hydrophobic group, and when the silicon nitride-containing wafer surface is surface-treated using a treatment liquid containing a silicon compound having a large hydrophobic group, the wafer surface after the treatment is good. Shows hydrophobicity. If the total number of carbon atoms contained as R 1 in the formula [II-1] is 6 or more, the wafer surface containing silicon nitride can be sufficiently hydrophobized.
  • the functional group represented by X which is the reactive site can chemically react with the hydroxyl group on the wafer surface.
  • the silicon element of the silicon compound is chemically bonded to the silicon element on the wafer surface, and can impart hydrophobicity to the wafer surface.
  • Examples of the silicon compound represented by the general formula [II-1] include C 4 H 9 (CH 3 ) 2 SiCl, C 5 H 11 (CH 3 ) 2 SiCl, C 6 H 13 (CH 3 ) 2 SiCl, C 7 H 15 (CH 3 ) 2 SiCl, C 8 H 17 (CH 3 ) 2 SiCl, C 9 H 19 (CH 3 ) 2 SiCl, C 10 H 21 (CH 3 ) 2 SiCl, C 11 H 23 (CH 3 ) 2 SiCl, C 12 H 25 (CH 3 ) 2 SiCl, C 13 H 27 (CH 3 ) 2 SiCl, C 14 H 29 (CH 3 ) 2 SiCl, C 15 H 31 (CH 3 ) 2 SiCl, C 16 H 33 (CH 3 ) 2 SiCl, C 17 H 35 (CH 3 ) 2 SiCl, C 18 H 37 (CH 3 ) 2 SiCl, C 5 H 11 (CH 3 ) HSiCl, C 6 H 13 (CH 3 ) HSiC
  • the halogen atom to be substituted is preferably a fluorine atom in consideration of the hydrophobizing performance.
  • the monovalent functional group represented by X in the general formula [II-1] whose element bonded to the silicon element is nitrogen is carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium , Fluorine, chlorine, bromine, iodine, or any other functional group, for example, —NHSi (CH 3 ) 3 group, —NHSi (CH 3 ) 2 C 4 H 9 group, —NHSi (CH 3 ) 2 C 8 H 17 group, —N (CH 3 ) 2 group, —N (C 2 H 5 ) 2 group, —N (C 3 H 7 ) 2 group, —N (CH 3 ) (C 2 H 5 ) group, —NH (C 2 H 5 ) group, —NCO group, imidazole group, acetamide group and the like.
  • the monovalent functional group represented by X in the general formula [II-1] in which the element bonded to the silicon element is oxygen is carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium.
  • Fluorine, chlorine, bromine, iodine, or any other functional group may be used.
  • —OCH 3 group, —OC 2 H 5 group, —OC 3 H 7 group, —OCOCH 3 group, —OCOCF 3 groups are listed.
  • the halogen group represented by X in the general formula [II-1] includes —F group, —Cl group, —Br group, —I group and the like. Of these, a —Cl group is more preferred.
  • a may be an integer of 1 to 3, but when a is 1 or 2, if the surface treatment agent for silicon nitride-containing wafers is stored for a long period of time, moisture may be mixed. Since the polymerization of the silicon compound occurs and the hydrophobicity-imparting effect may be reduced, the storage period may be shortened.
  • the treatment agent is dissolved in a diluent solvent to form a surface treatment solution for a silicon nitride-containing wafer, the treatment solution is mixed with moisture in the atmosphere during use, and polymerization of the silicon compound occurs. Insoluble substances may be deposited in the treatment liquid.
  • those having a of 3 in the general formula [II-1] that is, silicon represented by the general formula [II-2]) Compound
  • R 1 is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms or a hydrogen atom in which a hydrogen atom may be substituted with a halogen atom;
  • a compound composed of two methyl groups (that is, a silicon compound represented by the general formula [II-3]) is preferable because of its high reaction rate with hydroxyl groups on the wafer surface. This is because the steric hindrance due to the hydrophobic group has a great influence on the reaction rate in the reaction between the hydroxyl group on the wafer surface and the silicon compound, and the alkyl chain bonded to the silicon element has the remaining two except the longest one. This is because a shorter one is preferable.
  • preferable examples of the silicon compound represented by the general formula [II-1] described above include, for example, C 4 H 9 (CH 3 ) 2 SiCl, C 5 H 11 (CH 3 ) 2 SiCl, C 6 H 13 (CH 3 ) 2 SiCl, C 7 H 15 (CH 3 ) 2 SiCl, C 8 H 17 (CH 3 ) 2 SiCl, C 9 H 19 (CH 3 ) 2 SiCl, C 10 H 21 (CH 3 ) 2 SiCl, C 11 H 23 (CH 3 ) 2 SiCl, C 12 H 25 (CH 3 ) 2 SiCl, C 13 H 27 (CH 3 ) 2 SiCl, C 14 H 29 (CH 3 ) 2 SiCl, C 15 H 31 (CH 3 ) 2 SiCl, C 16 H 33 (CH 3 ) 2 SiCl, C 17 H 35 (CH 3 ) 2 SiCl, C 18 H 37 (CH 3 ) 2 SiCl, C 2 F 5 C 2 H 4 (CH 3) 2 SiCl,
  • the surface treatment agent for a silicon nitride-containing wafer is a silicon compound represented by the general formula [II-4], it is possible to impart excellent hydrophobicity to the silicon nitride-containing wafer surface, resulting in a shorter time. It is preferable because sufficient hydrophobicity can be imparted by the treatment.
  • the surface treatment solution for a silicon nitride-containing wafer according to the present invention only needs to contain at least the above-mentioned surface treatment agent for a silicon nitride-containing wafer, and may contain two or more kinds of the treatment agents.
  • the treating agent is dissolved in a diluting solvent.
  • the dilution solvent is not particularly limited as long as it dissolves the treatment agent.
  • Organic solvents such as polyhydric alcohol derivatives and nitrogen element-containing solvents are preferably used.
  • the reactive sites When water is used as a diluting solvent, the reactive sites (X in the general formula [II-1] and Y in the general formula [II-2]) are hydrolyzed by water. Thus, a silanol group (Si—OH) may be generated. Since the reactive site also reacts with the silanol group, silicon compounds may be bonded to each other to form a dimer. Since this dimer has low reactivity with the hydroxyl group on the wafer surface, it may take a long time to hydrophobize the wafer surface, so it is not preferable to use water as a diluting solvent.
  • Si—OH silanol group
  • the silicon compound easily reacts with a protic solvent, it is particularly preferable to use an aprotic solvent as the organic solvent because hydrophobicity is easily developed in a short time.
  • the aprotic solvent is both an aprotic polar solvent and an aprotic apolar solvent.
  • aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, lactone solvents, carbonate solvents, polyhydric alcohol derivatives having no hydroxyl group, N Examples thereof include nitrogen element-containing solvents having no —H bond.
  • hydrocarbons examples include toluene, benzene, xylene, hexane, heptane, and octane.
  • esters examples include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetoacetate, and the ether.
  • examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like
  • ketones examples include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, and cyclohexanone.
  • halogen-containing solvent examples include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, 1, 1, 1, 3, 3-pentane.
  • Hydrofluorocarbons such as fluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora H (manufactured by Nippon Zeon Co., Ltd.), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoro Hydrofluoroethers such as fluoroisobutyl ether, Asahiklin AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec7100, Nove7200, Novec7300, and Novec7600 (all from 3M), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, Chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-p
  • Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of the lactone solvents include ⁇ -butyrolactone, ⁇ -valero Lactone, ⁇ -caprolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ -undecanolactone, ⁇ -dodecanolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -octa Nolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ -undecanolactone, ⁇ -dodecanolactone, ⁇ - Examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.
  • Examples of the polyhydric alcohol derivative having no hydroxyl group include ethylene glycol dimethyl ether and ethylene glycol. Diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, di Tylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol Ethylene
  • a non-flammable solvent for a part or all of the dilution solvent because the processing liquid becomes non-flammable or the flash point becomes high, and the risk of the processing liquid is reduced.
  • Many of the halogen-containing solvents are nonflammable, and the nonflammable halogen-containing solvent can be suitably used as a nonflammable diluent solvent.
  • GHS International Harmonized System for Classification and Labeling of Chemicals
  • a solvent having a flash point of 93 ° C. or lower is defined as “flammable liquid”. Therefore, even if it is not a nonflammable solvent, if a solvent having a flash point exceeding 93 ° C. is used as the dilution solvent, the flash point of the treatment liquid tends to be 93 ° C. or higher, and the treatment liquid falls under “flammable liquid”. This is preferable from the viewpoint of safety.
  • lactone solvents since many lactone solvents, carbonate solvents and polyhydric alcohol derivatives have a high flash point, it is preferable to use them as solvents since the risk of the treatment liquid can be reduced.
  • the diluent solvent may be present as long as it is a trace amount of water.
  • the silicon compound may be hydrolyzed by the moisture to reduce the reactivity.
  • the amount of water in the solvent is preferably less than 1 mole in terms of molar ratio to the silicon compound when mixed with the silicon compound. It is particularly preferable to make it less than 5 mole times.
  • the silicon compound is preferably mixed so as to be 0.1 to 50% by mass with respect to 100% by mass of the total amount of the treatment liquid, and more preferably with respect to 100% by mass of the total amount of the treatment liquid. 0.3 to 20% by mass.
  • the silicon compound is less than 0.1% by mass, it reacts with moisture contained in a minute amount in the diluting solvent and is easily deactivated, so the ability to hydrophobize is poor and the wafer surface cannot be sufficiently hydrophobized. There is.
  • it is more than 50% by mass there is a concern that it remains as an impurity on the wafer surface, and it is not preferable from the viewpoint of cost.
  • the treatment liquid contains an acid because sufficient hydrophobicity can be imparted to the silicon nitride-containing wafer surface by a short time treatment.
  • the silicon compound represented by the following general formula [II-5] can be processed in a shorter time on the silicon nitride-containing wafer surface. It is preferable because sufficient hydrophobicity can be imparted.
  • R 4 (CH 3 ) 2 SiZ [II-5] [In the formula [II-5], R 4 is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • Z is a monovalent functional group in which the element bonded to the silicon element is nitrogen, or a monovalent functional group in which the element bonded to the silicon element is oxygen. ]
  • the acid promotes the reaction between the silicon compound and the hydroxyl group on the silicon nitride-containing wafer surface.
  • examples of such acids include water-free acids such as trifluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, and hydrogen chloride. It is done.
  • acids such as trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride, and the like are preferable. Preferably not.
  • the addition amount of the acid is preferably 0.01 to 100% by mass with respect to 100% by mass of the total amount of the silicon compound. If the amount added is small, the catalytic effect is lowered, which is not preferable. Moreover, even if it adds excessively, a catalyst effect will not improve, but when it increases more than a silicon compound, a catalyst effect may fall conversely. Furthermore, there is a concern that the impurities may remain on the wafer surface as impurities. For this reason, the addition amount of the acid is preferably 0.01 to 100% by mass, more preferably 0.1 to 50% by mass with respect to 100% by mass of the total amount of the silicon compound.
  • the treatment liquid may be ammonia, alkylamine, N, N, N ′, N ′, which promotes the reaction between the silicon compound and the hydroxyl group on the silicon nitride-containing wafer surface.
  • Bases such as tetramethylethylenediamine, triethylenediamine, dimethylaniline, pyridine, piperazine, N-alkylmorpholine, salts such as ammonium sulfide, potassium acetate, methylhydroxyamine hydrochloride, and metal complexes such as tin, aluminum, and titanium Metal salts may be included.
  • the carbon number of R 4 in the general formula [II-5] is 6 to 18 because excellent hydrophobicity can be imparted to the silicon nitride-containing wafer surface.
  • Z in the general formula [II-5] is a monovalent functional group in which the element bonded to the silicon element is nitrogen
  • the reaction rate tends to be high, and as a result, the surface of the silicon nitride-containing wafer is short. It is preferable because excellent hydrophobicity is easily expressed over time.
  • the silicon compound that is a monovalent functional group in which Z is an element in which the element bonded to the silicon element is oxygen tends to be deactivated by a compound by-produced by reaction with the wafer surface or reaction with moisture. is there. On the other hand, such deactivation is unlikely to occur in a silicon compound having a monovalent functional group in which the element in which Z is bonded to the silicon element is nitrogen.
  • a silicon compound having a large number of carbon atoms in the hydrophobic group R 1 in the general formula [II-1] may have a decreased reactivity with the hydroxyl group on the silicon nitride-containing wafer surface due to the steric hindrance of R 1 .
  • the reaction between the hydroxyl group on the silicon nitride-containing wafer surface and the silicon compound is promoted, and this compensates for a decrease in reactivity due to steric hindrance due to the hydrophobic group.
  • the treatment liquid may be one liquid type in which the silicon compound and the acid are mixed from the beginning, or two liquids of the liquid containing the silicon compound and the liquid containing the acid. As a type, it may be mixed when used.
  • the wafer surface treatment method of the present invention will be described.
  • the wafer containing silicon nitride that is surface-treated using the treatment agent and the treatment liquid of the present invention include a silicon wafer and a silicon wafer on which a silicon nitride film is formed by CVD or sputtering.
  • a silicon nitride film may be formed on a wafer that does not contain a silicon element, such as a sapphire wafer, various compound semiconductor wafers, and a plastic wafer.
  • the treatment liquid can hydrophobize the surface of a wafer containing silicon nitride, the surface of a film containing silicon nitride formed on the wafer, and the like.
  • a wafer having a large amount of silicon nitride film or silicon nitride portion on the surface has few hydroxyl groups on the surface, and it has been difficult to impart hydrophobicity with conventional techniques.
  • the use of the treatment agent and the treatment liquid of the present invention can impart sufficient hydrophobicity to the wafer surface, which in turn has the effect of increasing the adhesion between the wafer surface and the resist. Therefore, a wafer having many silicon nitride films or silicon nitride portions on the surface is suitable for applying the processing liquid of the present invention. Note that the surface of the silicon nitride-containing wafer may be cleaned in advance before performing the wafer surface treatment method of the present invention.
  • the cleaning solution used for the cleaning examples include water, an organic solvent, a mixed solution of water and an organic solvent, and a solution in which an acid or a base is dissolved.
  • a silicon nitride-containing wafer may be immersed in a cleaning liquid, or the wafer is cleaned one by one by supplying the cleaning liquid to the vicinity of the rotation center while rotating the silicon nitride-containing wafer almost horizontally. Spin processing may be performed. Further, the cleaning liquid may be used in a heated state.
  • the present invention is the wafer surface treatment method for improving the adhesion between the wafer and the resist by hydrophobizing the wafer surface containing silicon nitride, Contact the wafer surface with a silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer surface treatment solution, or contact the wafer surface with a silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer surface treatment solution.
  • a surface treatment step for hydrophobizing the wafer surface A resist film forming step of forming a resist film on the wafer surface;
  • the surface of the wafer is contacted with a silicon nitride-containing wafer surface treatment agent or a silicon nitride-containing wafer surface treatment solution, or the silicon nitride-containing wafer surface treatment agent or silicon nitride-containing wafer is contacted with the wafer surface.
  • the surface of the wafer is brought into contact to make the wafer surface hydrophobic.
  • a gas obtained by bubbling the treatment agent or treatment solution with a gas such as nitrogen is sprayed on the wafer surface, or the treatment agent or treatment solution is vaporized under reduced pressure and / or heating.
  • a vapor treatment method for forming a wafer and adhering to the wafer surface is used, but not limited to the vapor treatment method, even if the treatment agent or the treatment liquid is directly contacted with the wafer surface. good. Since the liquid processing method can be performed continuously from the surface processing step to the resist film forming step by, for example, spin processing, it is considered to lead to simplification of the production process. Since the surface treatment agent for silicon nitride-containing wafers or the surface treatment liquid for silicon nitride-containing wafers of the present invention can impart sufficient hydrophobicity to the silicon nitride-containing wafer surface even in a liquid treatment method, There seems to be a big merit.
  • the method for supplying the surface treatment agent or the surface treatment liquid is not particularly limited, and the wafer surface and the surface treatment agent are used.
  • the surface treatment can be performed as long as the surface treatment liquid is in contact with the surface treatment liquid.
  • a spin process for processing the wafers one by one by supplying the processing agent or the processing liquid to the vicinity of the rotation center while rotating the wafer while holding the wafer substantially horizontal is more preferably used.
  • the surface treatment process when the temperature of the treatment agent or treatment liquid is increased, the surface treatment can be easily performed in a shorter time. However, if the temperature is too high, the stability of the treatment agent or treatment liquid may be impaired due to boiling or evaporation of the treatment agent or treatment solution, and therefore the temperature is 10 to 160 ° C. In particular, 15 to 120 ° C. is preferable.
  • a resist film forming step for forming a resist film on the wafer surface is performed.
  • the resist before curing may be supplied to the surface with the treatment agent or treatment liquid remaining on the wafer surface, and the treatment agent or treatment solution may be replaced with the resist.
  • a resist before curing may be supplied to the surface.
  • the wafer surface after the surface treatment step is washed with a solvent or water for particle removal or the like, and the uncured resist is supplied to the surface with the solvent or water remaining on the wafer surface.
  • the resist may be replaced with water, or after drying the solvent and water remaining on the cleaned wafer surface, the uncured resist may be supplied to the surface.
  • the method for forming the resist is not particularly limited, and a known method can be used. For example, a spin process in which the wafer is processed one by one by supplying the uncured resist near the center of rotation while holding the wafer substantially horizontal and rotating is more preferably used.
  • a general method for forming a fine pattern on the wafer surface through lithography, etching, etc. is to apply the resist on the wafer surface in the resist film forming step, and then apply a resist mask. Then, the resist is exposed to light, and the resist having a desired pattern is produced by etching away the exposed resist or the resist that has not been exposed.
  • a resist having a pattern can also be obtained by pressing a mold having a pattern against the resist. Subsequently, the wafer is etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, the resist is removed to obtain a wafer having a pattern.
  • the wafer surface containing silicon element was treated using the treatment liquid of the present invention, and the contact angle of the treated wafer surface with water was measured to evaluate the hydrophobicity of the treated wafer surface.
  • a silicon wafer with a smooth silicon oxide film as a wafer containing silicon element As a wafer containing silicon element; a silicon wafer having a thermal oxide film layer with a thickness of 1 ⁇ m on the surface (hereinafter simply referred to as “silicon wafer with silicon oxide film”)
  • a silicon wafer with a silicon nitride film manufactured by LP-CVD a silicon wafer having a silicon nitride layer with a thickness of 50 nm on the surface (hereinafter simply referred to as a “silicon wafer with a silicon nitride film”) In some cases).
  • Example I-1 (1) Preparation of surface treatment solution Hexamethyldisilazane [(CH 3 ) 3 SiNHSi (CH 3 ) 3 ] as a silicon compound; 3 g, trifluoroacetic anhydride [(CF 3 CO) 2 O] as an acid; 3 g, 96.7 g of propylene glycol monomethyl ether acetate (PGMEA) as a diluting solvent were mixed and stirred for about 5 minutes, and the concentration of silicon compound relative to the total amount of the surface treatment liquid (hereinafter referred to as “silicon compound concentration”) was A 3% by mass surface treatment solution was obtained.
  • PGMEA propylene glycol monomethyl ether acetate
  • a silicon wafer with a silicon oxide film was immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 2 minutes, then immersed in pure water at room temperature for 1 minute, and immersed in 2-propanol at room temperature for 1 minute.
  • a silicon wafer with a silicon nitride film is immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes at room temperature, then immersed in pure water for 1 minute at room temperature, and 28% by mass ammonia water: 30% by mass hydrogen peroxide solution at room temperature.
  • Water was mixed at a volume ratio of 1: 1: 5, immersed in a cleaning solution with a hot plate at a temperature of 70 ° C. for 1 minute, immersed in pure water at room temperature for 1 minute, and then in 2-propanol at room temperature for 1 minute. Soaked.
  • each of the obtained wafers was evaluated in the manner described in the above “contact angle evaluation method”. As shown in Table 1, in the silicon wafer with a silicon oxide film, the initial contact angle before the surface treatment was less than 10 °. However, the contact angle after the surface treatment was 88 °, indicating excellent hydrophobicity. Moreover, in the silicon wafer with a silicon nitride film, the initial contact angle before the surface treatment was less than 10 °, but the contact angle after the surface treatment was 58 °, indicating hydrophobicity.
  • Examples I-2 to I-3 The silicon compound and acid used in Example I-1 were appropriately changed, and the wafer was surface treated and further evaluated. The results are shown in Table 1.
  • (CH 3 ) 3 SiN (CH 3 ) 2 is trimethylsilyldimethylamine
  • [CF 3 (CH 2 ) 2 (CH 3 ) 2 Si] 2 NH is bistrifluoropropyldimethylsilazane
  • CF 3 COOH is trifluoroacetic acid. Show.
  • Example I-4 Butyldimethylsilyldimethylamine [C 4 H 9 (CH 3 ) 2 SiN (CH 3 ) 2 ] as a silicon compound; 1 g, trifluoroacetic acid [CF 3 COOH] as an acid; 0.1 g, PGMEA as a diluting solvent; 9 g was mixed and stirred for about 5 minutes to prepare a surface treatment solution. Furthermore, the immersion time of each wafer in the surface treatment liquid was set to 10 minutes. The rest is the same as Example I-1. As shown in Table 1, the evaluation results of the silicon wafer with the silicon oxide film showed an excellent hydrophobicity with a contact angle of 87 ° after the surface treatment. Moreover, the evaluation result of the silicon wafer with a silicon nitride film was as shown in Table 1, and the contact angle after the surface treatment was 71 °, indicating excellent hydrophobicity.
  • Example I-5 to I-25 The silicon compound, silicon compound concentration, acid, acid concentration, dilution solvent, immersion time of each wafer in the surface treatment solution, and immersion temperature of each wafer in the surface treatment solution used in Example I-4 were appropriately changed. Then, the wafer was surface-treated and further evaluated. The results are shown in Table 1.
  • C 8 H 17 (CH 3 ) 2 SiN (CH 3 ) 2 means octyldimethylsilyldimethylamine
  • Novec7100 / PGMEA is hydrofluoroether (3M Novec7100) and PGMEA.
  • Example I-26 (1) Preparation of surface treatment liquid A surface treatment liquid similar to that in Example I-6 was prepared.
  • each of the obtained wafers was evaluated in the manner described in the above “contact angle evaluation method”. As shown in Table 1, in the silicon wafer with a silicon oxide film, the initial contact angle before the surface treatment was less than 10 °. However, the contact angle after the surface treatment was 101 °, indicating excellent hydrophobicity. Moreover, in the silicon wafer with a silicon nitride film, the initial contact angle before the surface treatment was less than 10 °, but the contact angle after the surface treatment was 85 °, indicating excellent hydrophobicity. If the surface treatment process is performed by the spin treatment as described above, the process liquid removal process of the next process and the subsequent resist film forming process can be continuously performed, which leads to simplification of the production process. As a result, it contributes to the improvement of the throughput.
  • Example I-27 Octylsilyltrisdimethylamine [C 8 H 17 Si [N (CH 3 ) 2 ] 3 ] as a silicon compound; 1 g, trifluoroacetic anhydride [(CF 3 CO) 2 O] as an acid; 0.1 g, dilution solvent was mixed with 98.9 g and stirred for about 5 minutes to prepare a surface treatment solution. The rest is the same as Example I-1. As shown in Table 1, the evaluation results of the silicon wafer with the silicon oxide film showed a contact angle of 93 ° after the surface treatment, indicating excellent hydrophobicity.
  • the evaluation result of the silicon wafer with the silicon nitride film showed an excellent hydrophobicity with a contact angle of 87 ° after the surface treatment.
  • a white solid was deposited as a precipitate in the treatment liquid. This is considered that insoluble matter was generated due to the progress of the polymerization of the silicon compound due to the mixing of moisture in the atmosphere into the treatment liquid.
  • the above solid precipitation did not occur.
  • the vapor prime method was simply reproduced, and the wafer was surface-treated. Although the exact temperature of the steam is unknown, it is considered that the boiling point of Novec 7100, 61 ° C., is exceeded.
  • Table 1 the evaluation result of the silicon wafer with the silicon oxide film shows that the contact angle after the surface treatment is 81 ° and exhibits excellent hydrophobicity, but the energy is higher than that of the surface treatment method in which the treatment liquid is brought into contact with the wafer. Loss was great.
  • the evaluation result of the silicon wafer with the silicon nitride film was 46 ° after the surface treatment, and the hydrophobicity was not sufficient.
  • the evaluation result of the silicon wafer with a silicon nitride film was that the contact angle after the surface treatment was 36 °, and the hydrophobicity was not sufficient.
  • Examples I-1 to I-27 using the treatment liquid containing the acid, the diluting solvent, and the silicon compound represented by the general formula [I-1] the surface treatment for bringing the treatment liquid into contact with the wafer is performed.
  • hydrophobicity could be imparted to the wafer surface.
  • Examples I-1 to I-26 using a treatment liquid containing an acid, a diluting solvent, and the silicon compound represented by the general formula [I-2] the wafer surface can be imparted with hydrophobicity, and the treatment liquid Was left in the atmosphere, no insoluble matter was precipitated in the treatment solution.
  • Examples I-4 to I-26 using a treatment liquid containing an acid, a diluting solvent and the silicon compound represented by the above general formula [I-3] excellent hydrophobicity can be imparted to the wafer surface. did it. Further, in Examples I-6 to I-26 using a treatment liquid containing an acid, a diluting solvent, and a silicon compound in which R 2 of the general formula [I-3] has 6 to 18 carbon atoms, Excellent hydrophobicity could be imparted.
  • the method of treating the surface of the wafer in the above example had less energy loss associated with the surface treatment for hydrophobizing the wafer surface than the conventional vapor prime method that was simply reproduced in Comparative Example I-1.
  • the spin treatment in which the wafer is surface-treated in Example I-26 can continuously perform the surface treatment step, the treatment liquid removal step, and the resist film formation step of the present invention. In comparison, the throughput was good.
  • Comparative Example I-1 although silicon wafer with silicon oxide film having a large number of hydroxyl groups per unit area could impart excellent hydrophobicity, silicon with silicon nitride film having a small number of hydroxyl groups per unit area In contrast to the fact that sufficient hydrophobicity could not be imparted to the wafer, in the above embodiment, hydrophobicity was imparted to both the silicon wafer with a silicon oxide film and the silicon wafer with a silicon nitride film. could be granted.
  • the hydrophobicity of the treated wafer surface was evaluated by treating the silicon nitride-containing wafer surface with the treatment agent or treatment liquid of the present invention and measuring the contact angle of the treated wafer surface with water.
  • Example II-1 (1) Preparation of surface treatment solution for silicon nitride-containing wafer
  • Nonafluorohexyldimethylchlorosilane [C 4 F 9 (CH 2 ) 2 (CH 3 ) 2 SiCl] as a silicon compound
  • 1 g hydrofluoroether (manufactured by 3M) as a diluting solvent Novec7100);
  • 96 g propylene glycol monomethyl ether acetate (PGMEA); 3 g are mixed (the solvent is indicated as Novec7100 / PGMEA-3 in Table 2), and stirred for about 5 minutes to obtain silicon relative to the total amount of the surface treatment solution.
  • a surface treatment solution for a silicon nitride-containing wafer having a compound concentration (hereinafter referred to as “silicon compound concentration”) of 1% by mass was obtained.
  • a silicon wafer with a smooth silicon nitride film (smooth silicon wafer having a silicon nitride layer with a thickness of 50 nm on the surface) produced by LP-CVD is used at room temperature for a 1% by mass hydrofluoric acid aqueous solution. 2 minutes, then immersed in pure water for 1 minute at room temperature, mixed with 28% by weight ammonia water: 30% by weight hydrogen peroxide water: water at a volume ratio of 1: 1: 5, and the liquid temperature on a hot plate was immersed in a cleaning solution at 70 ° C. for 1 minute, immersed in pure water at room temperature for 1 minute, and immersed in 2-propanol at room temperature for 1 minute.
  • Example II-2 to II-3 The dilution solvent used in Example II-1 was appropriately changed, and the wafer surface treatment was performed in the same procedure as in Example II-1, and further evaluated. The results are shown in Table 2.
  • CTFP / PGMEA means a solvent using 1-chloro-3,3,3-trifluoropropene (CTFP) instead of Novec7100 in Example II-1
  • DCTFP / PGMEA means A solvent using cis-1,2-dichloro-3,3,3-trifluoropropene (DCTFP) instead of Novec7100 in Example II-1 is meant.
  • Example II-4 As a silicon compound, octyldimethylchlorosilane [C 8 H 17 (CH 3 ) 2 SiCl]; 10 g, hydrofluoroether (3M Novec7100) as a diluent solvent; 80 g, propylene glycol monomethyl ether acetate (PGMEA); 10 g ( The solvent is expressed as “Novec7100 / PGMEA-10” in Table 2) and stirred for about 5 minutes to obtain a surface treatment solution for a silicon nitride-containing wafer having a silicon compound concentration of 10 mass% with respect to the total amount of the surface treatment solution. .
  • PGMEA propylene glycol monomethyl ether acetate
  • the silicon wafer with the silicon nitride film was immersed in the treatment liquid at 20 ° C. for 60 minutes.
  • Other processes are the same as those in Example II-1.
  • the obtained wafer was evaluated in the manner described in the above “contact angle evaluation method”, as shown in Table 2, the initial contact angle before the surface treatment was less than 10 °. The angle was 75 °, indicating excellent hydrophobicity.
  • Example II-5 Octyldimethylsilyldimethylamine [C 8 H 17 (CH 3 ) 2 SiN (CH 3 ) 2 ] as a silicon compound; 1 g, PGMEA as a diluting solvent; 98.9 g, and trifluoroacetic acid [CF 3 COOH] as an acid; 0 0.1 g was mixed and stirred for about 5 minutes to obtain a silicon nitride-containing wafer surface treatment solution having a silicon compound concentration of 1% by mass.
  • the amount of the acid added to the total amount of the silicon compound of 100% by mass (hereinafter referred to as acid concentration) is 10% by mass.
  • the rest is the same as Example II-1.
  • the evaluation result showed that the contact angle after the surface treatment was 86 °, indicating excellent hydrophobicity.
  • Example II-6 to II-24, II-27 to II-29 The surface treatment of the wafer was performed by appropriately changing the silicon compound, silicon compound concentration, acid, acid concentration, dilution solvent, surface treatment time, and surface treatment temperature used in Example II-5, and the evaluation was further performed. It was. The results are shown in Table 2.
  • C 4 H 9 (CH 3 ) 2 SiN (CH 3 ) 2 means butyldimethylsilyldimethylamine
  • (CF 3 CO) 2 O means trifluoroacetic anhydride.
  • Example II-26 (1) Preparation of silicon nitride-containing wafer surface treatment solution A silicon nitride-containing wafer surface treatment solution similar to Example II-5 was prepared.
  • the exact temperature of the steam is not known, it is considered to be 61 ° C. or higher, which is the boiling point of Novec7100.
  • the contact angle after the surface treatment was 46 ° and the hydrophobicity was low, as shown in Table 2.
  • Example II-2 The same as Example II-5 except that 1 g of bistrifluoropropyldimethylsilazane [[CF 3 (CH 2 ) 2 (CH 3 ) 2 Si] 2 NH]; 1 g) was used as the silicon compound. As shown in Table 2, the contact angle after the surface treatment was 62 °.
  • Examples II-1 to II-29 using the treatment liquid containing the silicon compound represented by the general formula [II-1] hydrophobicity can be imparted to the silicon nitride-containing wafer surface. It was. Furthermore, in Examples II-1 to II-24 and II-26 to II-29 using the treatment liquid containing the silicon compound represented by the general formula [II-2], hydrophobicity is imparted to the silicon nitride-containing wafer surface. In addition, even when the treatment liquid was allowed to stand in the atmosphere, no insoluble matter was precipitated in the treatment liquid.
  • Examples II-1 to II-24 and II-26 to II-29 using the treatment liquid containing the silicon compound represented by the general formula [II-3] the surface of the wafer was hydrophobicized in a shorter time. It was possible to impart sex.
  • Examples II-1 to II-3 using the treatment liquid containing the silicon compound represented by the general formula [II-4] it is possible to impart more excellent hydrophobicity to the wafer surface in a shorter time. I was able to.
  • Examples II-5 to II-24 and II-26 to II-28 using the treatment liquid containing the silicon compound represented by the general formula [II-5] the surface of the wafer was hydrophobicized in a shorter time. It was possible to impart sex.
  • Examples II-5 to II-24 and II-26 using a treatment liquid containing a silicon compound in which R 4 of the general formula [II-5] has 6 to 18 carbon atoms the wafer surface is more excellent. It was possible to impart hydrophobicity. Further, Examples II-5 to II-24, II— using a treatment liquid containing a silicon compound in which Z in the general formula [II-5] is a monovalent functional group in which the element bonded to the silicon element is nitrogen is used. In No. 26, excellent hydrophobicity could be imparted to the wafer surface. On the other hand, in Comparative Examples II-1 and II-2, sufficient hydrophobicity could not be imparted to the silicon nitride-containing wafer surface. In addition, Examples II-1 to II-29 were able to impart even better hydrophobicity than Reference Examples II-1 to II-2.

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Abstract

L'invention concerne un procédé de traitement de surface d'une tranche contenant du silicium élémentaire dans lequel une surface de tranche contenant du silicium élémentaire est rendue hydrophobe pour augmenter l'adhérence entre ladite tranche et une réserve. Ledit procédé comprend les étapes suivantes : le traitement de surface pour rendre la tranche hydrophobe en amenant un liquide de traitement de surface de tranche contenant du silicium élémentaire en contact avec la surface de la tranche ; l'élimination du liquide de traitement de la surface de la tranche ; la formation de réserve sur la surface de la tranche. Ce procédé est caractérisé en ce qu'un liquide de traitement de surface de tranche contenant du silicium élémentaire, contenant un composé de silicium représenté par la formule générale (I-1), un acide et un solvant diluant est utilisé dans l'étape de traitement de surface. (I-1) R1 aSiX4−a (Dans ladite formule (I-1), chaque R1 représente indépendamment soit un groupe hydrogène, soit un groupe hydrocarboné en C1-18 dans lequel un atome d'hydrogène peut être remplacé par un atome d'halogène ; chaque X représente indépendamment un groupe fonctionnel monovalent, dont l'azote est l'élément qui se lie au silicium élémentaire, et a représente un entier de 1 à 3.)
PCT/JP2012/077950 2011-11-11 2012-10-30 Procédé de traitement d'une surface de tranche et liquide de traitement de surface, agent de traitement de surface et liquide de traitement de surface, procédé de traitement de surface pour des tranches contenant du nitrure de silicium Ceased WO2013069499A1 (fr)

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CN110462525B (zh) * 2017-03-24 2024-07-26 富士胶片电子材料美国有限公司 表面处理方法及用于所述方法的组合物
KR102391370B1 (ko) * 2018-04-05 2022-04-27 샌트랄 글래스 컴퍼니 리미티드 웨이퍼의 표면 처리 방법 및 당해 방법에 이용하는 조성물
KR102074223B1 (ko) 2018-09-10 2020-02-07 (주)신우에이엔티 기판 처리 장치용 유기화합물 분해 제거 구조

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WO2010047196A1 (fr) * 2008-10-21 2010-04-29 東京応化工業株式会社 Liquide de traitement de surface, procédé de traitement de surface, procédé d’hydrophobisation et substrat hydrophobisé
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