WO2021039165A1 - パターン形成方法およびその方法を含んだ半導体の製造方法 - Google Patents

パターン形成方法およびその方法を含んだ半導体の製造方法 Download PDF

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Publication number
WO2021039165A1
WO2021039165A1 PCT/JP2020/027357 JP2020027357W WO2021039165A1 WO 2021039165 A1 WO2021039165 A1 WO 2021039165A1 JP 2020027357 W JP2020027357 W JP 2020027357W WO 2021039165 A1 WO2021039165 A1 WO 2021039165A1
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Prior art keywords
film
pattern
hemicellulose
forming method
pattern forming
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Application number
PCT/JP2020/027357
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English (en)
French (fr)
Japanese (ja)
Inventor
将彦 春本
知佐世 毛利
田中　裕二
洋 有澤
正也 浅井
智大 本野
加藤　慎一
光 河原▲崎▼
英昭 谷村
貴美子 服部
和代 森田
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
王子ホールディングス株式会社
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Publication of WO2021039165A1 publication Critical patent/WO2021039165A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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

Definitions

  • the present invention relates to a pattern forming method for forming a pattern by forming a hard mask on a thin plate-shaped precision electronic substrate (hereinafter, simply referred to as "substrate”) such as a semiconductor wafer, and a semiconductor manufacturing method including the method.
  • substrate thin plate-shaped precision electronic substrate
  • semiconductor manufacturing method including the method.
  • a hard mask with excellent resistance may be used for dry etching of semiconductor substrates.
  • Hardmasks are used, for example, to form high-aspect patterns during the manufacture of 3D memories.
  • amorphous carbon has been used as a material for a hard mask (see Patent Documents 1 and 2).
  • Next-generation lithography requires a hard mask with a high etching selectivity.
  • the etching resistance is low simply by forming the SOC film on the substrate and patterning it, and the etching selection ratio is not sufficient as compared with the conventional amorphous carbon hard mask.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a pattern forming method capable of obtaining a mask of a resin film having excellent etching resistance.
  • a first aspect of the present invention is a first film forming step of coating and forming a resin film containing a polymer containing an oxygen atom on a substrate in a pattern forming method for forming a pattern on a substrate.
  • a lithography step a first etching step of transferring the pattern to the silicon-containing film by etching using the resist film as a mask, and a second etching step of transferring the pattern to the resin film by etching using the silicon-containing film as a mask.
  • an impregnation step of impregnating the surface of the resin film to which the pattern is transferred in a gas containing a metal atom with a metal.
  • the second aspect is the pattern forming method according to the first aspect, wherein the impregnation step includes a first heating step of heating the substrate in a gas containing the metal atom.
  • the third aspect further includes, in the pattern forming method according to the second aspect, a second heating step of heating the resin film to a predetermined temperature or more for 1 second or less after the impregnation step.
  • the resin film is irradiated with flash light or laser light.
  • a fifth aspect is the pattern forming method according to any one of the first to fourth aspects.
  • the pattern is printed on the resist film by exposure and the pattern is developed. It includes a developing step of forming on the resist film.
  • the oxygen atom content of the polymer is 20% by mass or more with respect to the total mass of the polymer.
  • the polymer contains a unit derived from a sugar derivative.
  • the polymer in the pattern forming method according to the seventh aspect, is hemicellulose.
  • the ninth aspect is a semiconductor manufacturing method including the pattern forming method according to any one of the first to eighth aspects.
  • the surface of the resin film to which the pattern is transferred is impregnated with metal in a gas containing metal atoms, so that the metal reacts with the resin to form the resin film. Can be cured, and a resin film mask having excellent etching resistance can be obtained.
  • the metal diffuses in the resin film and cures the entire resin film. be able to.
  • hemicellulose means a resin containing a unit derived from a sugar derivative such as xylose that constitutes hemicellulose.
  • the sugar derivative can be extracted from plants, wood and the like, and can be produced, for example, by the method described in International Publication No. 2019/012716.
  • FIG. 1 and each subsequent drawing the dimensions and numbers of each part are exaggerated or simplified as necessary for easy understanding.
  • FIGS. 1 and 2 are flowcharts showing a processing procedure of the pattern forming method according to the present invention.
  • the semiconductor wafer W is used as a processing target, and the pattern forming method according to the present invention can be implemented as a semiconductor manufacturing method and is included in the semiconductor manufacturing method.
  • an underlayer film is formed on the surface of the semiconductor wafer W to be processed.
  • FIG. 3 is a diagram showing a cross-sectional structure of the semiconductor wafer W to be processed.
  • the underlayer film 20 is formed on the base material 10 of silicon (Si).
  • the underlayer film 20 is, for example, a multilayer film in which thin films of silicon dioxide (SiO 2 ) and thin films of silicon nitride (SiN) are alternately laminated.
  • the underlayer film 20 is deposited on the base material 10 by, for example, CVD to form a film.
  • the underlayer film 20 may be amorphous silicon. By forming deep holes in the underlayer film 20 by etching, for example, a 3D-NAND flash memory is manufactured.
  • FIG. 4 is a diagram showing a cross-sectional structure of the semiconductor wafer W on which the hemicellulose film 30 is formed.
  • the hemicellulose membrane 30 is formed by a known spin coating method. Specifically, while the semiconductor wafer W as shown in FIG. 3 is rotated, the coating liquid containing hemicellulose is discharged onto the upper surface of the underlayer film 20. The coating liquid is spread on the upper surface of the underlayer film 20 by centrifugal force to form a coating film. The hemicellulose film 30 is formed on the lower layer film 20 by drying the coating film.
  • FIG. 5 is a diagram showing a cross-sectional structure of the semiconductor wafer W on which the silicon-containing film 40 is formed.
  • the silicon-containing film 40 is also formed by the spin coating method. That is, while the semiconductor wafer W as shown in FIG. 4 is rotated, the coating liquid of the polymer containing silicon is discharged onto the upper surface of the hemicellulose film 30. The coating liquid is uniformly spread on the upper surface of the hemicellulose film 30 by centrifugal force to form a coating film, and the coating film is dried to form a silicon-containing film 40 on the hemicellulose film 30.
  • the silicon-containing film may be formed by CVD (Chemical Vapor Deposition) instead of the spin coating method.
  • FIG. 6 is a diagram showing a cross-sectional structure of the semiconductor wafer W on which the resist film 50 is formed.
  • the resist film 50 is also formed by the spin coating method. That is, while the semiconductor wafer W having the structure as shown in FIG. 5 is rotated, the photoresist is discharged onto the upper surface of the silicon-containing film 40. In this embodiment, a chemically amplified photoresist is used.
  • the photoresist liquidated on the upper surface of the silicon-containing film 40 is spread on the upper surface of the silicon-containing film 40 by centrifugal force to form a coating film, and the coating film is dried to form a resist film 50 on the silicon-containing film 40. Is formed.
  • step S4 the exposure process of the resist film 50 is performed (step S4).
  • the pattern is printed on the resist film 50 by projecting and exposing the pattern of the reticle using an exposure machine (stepper).
  • the exposure machine exposes the resist film 50 using, for example, an ArF excimer laser as a light source.
  • an acid is generated in the exposed region irradiated with light.
  • a post-exposure bake process (PEB: Post Exposure Bake) is performed (step S5).
  • PEB Post Exposure Bake
  • the acid generated in the resist film 50 during exposure is diffused into the exposed region, and the deprotection reaction of the resist resin proceeds. If the resist film 50 is not a chemically amplified resist, post-exposure baking treatment is not required.
  • step S6 After the exposure and the baking process, the developing process is performed (step S6).
  • a developer is supplied to the resist film 50 to dissolve the exposed region, thereby forming the pattern exposed in the above exposure step on the resist film 50.
  • FIG. 7 is a diagram showing a cross-sectional structure of the semiconductor wafer W in which a pattern is formed on the resist film 50.
  • the steps from step S4 to step S6 are so-called photolithography steps, in which a pattern is formed on the resist film 50 by this photolithography step.
  • step S7 the silicon-containing film 40 is etched using the resist film 50 on which the pattern is formed as a mask (step S7).
  • the etching process in step S7 is performed by reactive ion etching (RIE: Reactive Ion Etching) using a fluorine-based gas as the etching gas.
  • RIE reactive ion etching
  • FIG. 8 is a diagram showing a cross-sectional structure of the semiconductor wafer W in which the pattern is transferred to the silicon-containing film 40. The same pattern formed on the resist film 50 is also formed on the silicon-containing film 40.
  • the hemicellulose film 30 is etched using the silicon-containing film 40 to which the pattern has been transferred as a mask (step S8).
  • the etching process in step S8 is performed by reactive ion etching using an oxygen-based gas as the etching gas.
  • the pattern formed on the silicon-containing film 40 is transferred to the hemicellulose film 30. Since the hemicellulose film 30 is not cured at this stage, the hemicellulose film 30 is relatively easily etched.
  • FIG. 9 is a diagram showing a cross-sectional structure of the semiconductor wafer W in which the pattern is transferred to the hemicellulose film 30. The same pattern formed on the resist film 50 by the photolithography process is also formed on the hemicellulose film 30 via the silicon-containing film 40.
  • step S9 the hemicellulose membrane 30 is impregnated with metal (step S9).
  • This treatment proceeds by heating the semiconductor wafer W in which the pattern is formed on the hemicellulose film 30 in an atmospheric gas containing trimethylaluminum (TMA: Trimethylaluminium).
  • TMA trimethylaluminum
  • the heating temperature of the semiconductor wafer W at this time is 20 ° C. or higher and 400 ° C. or lower.
  • the heating time is 30 seconds or more and 60 minutes or less.
  • the surface of the hemicellulose membrane 30 is impregnated with metallic aluminum (Al).
  • FIG. 10 is a diagram showing a cross-sectional structure of a semiconductor wafer W in which the surface of the hemicellulose film 30 is impregnated with aluminum.
  • the hemicellulose membrane 30 whose surface is impregnated with aluminum is heat-treated for a short time (step S10). Specifically, the hemicellulose membrane 30 impregnated with aluminum is heated for 1 second or less.
  • flash lamp annealing FLA: Flash Lamp Anneal
  • the semiconductor wafer W in which the surface of the hemicellulose film 30 as shown in FIG. 10 is impregnated with aluminum is carried into the flash lamp annealing apparatus.
  • the surface of the semiconductor wafer W is irradiated with flash light from a xenon flash lamp.
  • the irradiation time of the flash light is 0.1 ms to 100 ms.
  • the flash light is irradiated from the flash lamp with an irradiation time of, for example, 0.8 ms.
  • FIG. 11 is a diagram schematically showing a cross-sectional structure of a semiconductor wafer W in which aluminum is diffused in the hemicellulose film 30.
  • the hemicellulose membrane 30 may be heated above the thermal decomposition temperature of hemicellulose.
  • the time during which the hemicellulose film 30 is above the thermal decomposition temperature is 1 second or less, so that the aluminum is not thermally decomposed by the hemicellulose film 30. Diffuses through the membrane. Further, the higher the temperature reached by the hemicellulose film 30 during flash light irradiation, the easier it is for aluminum to diffuse in the film.
  • Hemicellulose is a resin containing many oxygen atoms in the form of OH groups.
  • aluminum diffuses in the hemicellulose film 30 and reacts with oxygen atoms of the hemicellulose, so that the entire hemicellulose film 30 is cured and the etching resistance is improved.
  • the hemicellulose film 30 acquires the characteristics required as a hard mask (high etching selectivity, etc.).
  • FIG. 12 is a diagram showing a cross-sectional structure of the semiconductor wafer W in which a pattern is formed on the underlayer film 20.
  • a pattern is formed on the hemicellulose film 30 by photolithography and etching techniques.
  • Simply forming a pattern on the hemicellulose film 30 has low etching resistance of the hemicellulose film 30, and it is difficult to use the hemicellulose film 30 as a hard mask. Therefore, the hemicellulose film 30 is impregnated with aluminum and the aluminum is diffused by flash lamp annealing to cure the hemicellulose film 30 and enhance the etching resistance.
  • a hard mask of a resin film (hemicellulose film 30) having excellent etching resistance can be obtained, and the lower layer film 20 can be etched using the hemicellulose film 30 as a mask.
  • Hemicellulose is a resin containing many oxygen atoms. Therefore, etching for forming a pattern is easy as compared with amorphous carbon which has been conventionally used as a material for a hard mask. Therefore, the film thickness of the silicon-containing film 40 for etching the hemicellulose film 30 can be reduced, and as a result, the resist film 50 can also be thinned, which is advantageous for pattern collapse and miniaturization.
  • hemicellulose containing many oxygen atoms has a property of easily reacting with a metal such as aluminum. Because of its properties, the hemicellulose membrane 30 can be cured by impregnating the surface of the hemicellulose membrane 30 with aluminum and reacting. Furthermore, hemicellulose contained in the cell wall of plants is also an inexpensive material as compared with amorphous carbon. For these reasons, hemicellulose is suitable as a material for hard masks.
  • the present invention can be modified in various ways other than those described above without departing from the spirit of the present invention.
  • the hemicellulose film 30 is formed on the lower layer film 20, and the lower layer film 20 is etched using the hemicellulose film 30 as a mask, but the present invention is not limited to this, and the hemicellulose film 30 is used.
  • the silicon base material 10 itself may be etched.
  • the hemicellulose film 30 may be formed on the layer on which the pattern is to be formed.
  • the hemicellulose film 30 is impregnated with aluminum as a metal, but the present invention is not limited to this, and Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc. , Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, Sb , Te, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, Lu and other metals may be impregnated into the hemicellulose membrane 30. Even in this way, the hemicellulose membrane 30 can be cured to obtain the same effect as that of the above embodiment.
  • the semiconductor wafer W is heated in an atmosphere containing trimethylaluminum during the metal impregnation treatment of the hemicellulose membrane 30, but heating is not essential, and the atmosphere in which the hemicellulose membrane 30 contains trimethylaluminum is not essential. You may just touch. If the surface of the hemicellulose membrane 30 containing a large amount of oxygen atoms is brought into contact with an atmosphere containing trimethylaluminum without heating, the surface can be impregnated with aluminum.
  • the short-time heat treatment in step S10 is not an essential step. If the hemicellulose membrane 30 is impregnated with aluminum without flash lamp annealing, the reaction between the hemicellulose containing many oxygen atoms and aluminum proceeds to some extent, the hemicellulose membrane 30 is cured, and the etching required for the hemicellulose membrane 30 is performed. Resistance can be imparted. However, the reaction between hemicellulose and aluminum proceeds more and the hemicellulose membrane 30 can be sufficiently cured by performing a short-time heat treatment such as flash lamp annealing.
  • the short-time heat treatment in step S10 is not limited to flash lamp annealing, and may be, for example, laser annealing in which the surface of the semiconductor wafer W including the hemicellulose film 30 is irradiated with laser light. That is, the hemicellulose membrane 30 impregnated with aluminum may be heated to a predetermined temperature or higher for 1 second or longer.
  • the hemicellulose film 30 is formed as the resin film used for the hard mask, but the material of the resin film is not limited to hemicellulose. If the material of the resin film used for the hard mask is a polymer containing oxygen atoms and the oxygen atom content of the polymer is 20% by mass or more based on the total mass of the polymer (material 1). good.
  • the polymer preferably contains at least one selected from a unit derived from a sugar derivative and a unit derived from (meth) acrylate (material 2).
  • the polymer and the organic solvent are contained, the polymer has a polymerization part a and a polymerization part b, the heavy part a has a sugar derivative part, and the sugar derivative part is bentose. It is preferable that the polymerization part b is at least one of the derivative part and the hextose derivative part and does not have the sugar derivative part (material 3).
  • the polymer is (a) a unit derived from a sugar derivative, (b) a unit derived from a compound having an antireflection function, and (c) a compound capable of cross-coupling the polymer. It may include the unit from which it is derived.
  • Examples of Materials 1 to 3 include random polymers of sugar methacrylate and styrene (90:10) using PGMEA (propylene glycol monomethyl ether acetate) as a solvent. Further, examples of the materials 1 to 3 include random polymers of sugar methacrylate, methacrylate and styrene (120: 280: 278) using PGMEA as a solvent. In this polymer, methacrylate functions as a crosslinkable group. Further, as the material 4, a material having a structure as shown in FIG. 13 is exemplified.
  • the technique according to the present invention is suitable for a method of forming a pattern using a resin film as a hard mask and a method of manufacturing a semiconductor including the same, for example, manufacturing a 3D-NAND flash memory.
  • Base material 20 Underlayer film 30 Hemicellulose film 40 Silicon-containing film 50 Resist film W Semiconductor wafer

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Drying Of Semiconductors (AREA)
  • Thin Film Transistor (AREA)
PCT/JP2020/027357 2019-08-23 2020-07-14 パターン形成方法およびその方法を含んだ半導体の製造方法 WO2021039165A1 (ja)

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JP2019-152649 2019-08-23

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001284209A (ja) * 2000-03-30 2001-10-12 Toshiba Corp 多層レジストパターン形成方法及び半導体装置の製造方法
JP2001357565A (ja) * 2000-06-13 2001-12-26 Ricoh Co Ltd 光ディスク原盤の製造方法及び光ディスク原盤
JP2018077533A (ja) * 2013-08-23 2018-05-17 富士フイルム株式会社 積層体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001284209A (ja) * 2000-03-30 2001-10-12 Toshiba Corp 多層レジストパターン形成方法及び半導体装置の製造方法
JP2001357565A (ja) * 2000-06-13 2001-12-26 Ricoh Co Ltd 光ディスク原盤の製造方法及び光ディスク原盤
JP2018077533A (ja) * 2013-08-23 2018-05-17 富士フイルム株式会社 積層体

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