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WO2018196319A1 - Photorésine à nanopoints de carbone à effet fluorescent, et son procédé d'imagerie - Google Patents

Photorésine à nanopoints de carbone à effet fluorescent, et son procédé d'imagerie Download PDF

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Publication number
WO2018196319A1
WO2018196319A1 PCT/CN2017/109454 CN2017109454W WO2018196319A1 WO 2018196319 A1 WO2018196319 A1 WO 2018196319A1 CN 2017109454 W CN2017109454 W CN 2017109454W WO 2018196319 A1 WO2018196319 A1 WO 2018196319A1
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WIPO (PCT)
Prior art keywords
carbon nano
sugar
containing polymer
photoresist
electron beam
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Ceased
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PCT/CN2017/109454
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English (en)
Chinese (zh)
Inventor
陈高健
翁雨燕
李志运
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Suzhou University
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Suzhou University
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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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • 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
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only

Definitions

  • quantum dots With the development of optoelectronic technology, the device size has been gradually reduced, and nano-sized quantum dots can be used as a good base material in the next few decades.
  • the synthesis of quantum dots is mainly divided into two types: “top-down method” and “bottom-up method", that is, large-sized materials are ground, or small molecules are used as precursors.
  • top-down method and “bottom-up method”
  • bottom-up method that is, large-sized materials are ground, or small molecules are used as precursors.
  • the positioning and laying of quantum dots play a more important role in the realization of functions.
  • the object of the invention is to provide a carbon nano-dot photoresist with fluorescence effect and an imaging method thereof, and to complete the preparation and laying of quantum dots by one-step method, to break the bottleneck of precise positioning of quantum dots, and to solve the precise control of quantum dot positioning and configuration.
  • the problem is completed in one step.
  • a carbon nano-dot photoresist having a fluorescent effect comprising:
  • the mass ratio of the sugar-containing polymer to water is 1:10 to 1,000,000.
  • the sugar-containing polymer has a molecular weight of 800 to 1,000,000.
  • the structure of the sugar-containing polymer is as follows:
  • R 1 H, ⁇ CH 3 ;
  • R 2 or R 3 H, ⁇ CH 3 ,
  • R 4 a sugar ring (glucose ring, galactose ring, mannose ring and other polyhydroxy compounds conforming to the sugar definition);
  • R 5 H, ⁇ CH 3 ;
  • the concentration of the sugar-containing polymer photoresist solution is 0.1 mg/L to 100 g/L.
  • the method of coating the photoresist solution on the surface of the substrate to be processed is any one of a spin coating method and a dropping coating method, wherein the substrate is a silicon wafer, an ITO glass, and the surface has A gold plated quartz plate and a SiO 2 plate having a silver film plating on its surface.
  • the electron beam exposure conditions are: a voltage of 5 kV to 30 kV, a working distance of 5 mm to 20 mm, an aperture of 5 ⁇ m to 30 ⁇ m, and an exposure measurement of 1000 to 100,000 ⁇ C/cm 2 .
  • the sugar-containing polymer film forms carbon nano-dots at the exposure point, and the carbon nano-dots have a corresponding quantum fluorescence effect, and the fluorescence is generated under the excitation of the corresponding wavelength ultraviolet or visible light.
  • the position of the carbon nano-dots in the photoresist can be precisely positioned by the electron beam
  • the carbon dots are combined into an arbitrary pattern by electron beam exposure, and the exposed region has blue fluorescence under excitation of a specific wavelength.
  • FIG. 1 is a schematic view showing the steps of an image forming method of a carbon nano-dot photoresist having a fluorescent effect
  • FIG. 2 is an AFM characterization diagram of a carbon nano-dot photoresist pattern having a fluorescent effect of the present invention
  • Figure 3 is a precise map of the carbon nanodots with fluorescence effect of the present invention (SEM image and optical diagram at 405 nm excitation);
  • FIG. 4 is a block array fluorescence confocal diagram based on a sugar-containing polymer carbon dot of the present invention, and an ultraviolet absorption spectrum thereof and a fluorescence emission spectrum thereof.
  • the present invention provides a carbon nano-dot photoresist having a fluorescent effect, comprising a, a sugar-containing polymer for self-crosslinking under electron beam, a side chain having a sugar ring; b, a solvent: water.
  • the sugar-containing polymer is any one of a glucose homopolymer, a mannose homopolymer, a copolymer of glucose and methacrylic acid, and a copolymer of glucose and sodium p-styrenesulfonate.
  • the mass ratio of the sugar-containing polymer to water is 1:10 to 1,000,000, and the structure of the sugar-containing polymer is as follows:
  • R 1 H, ⁇ CH 3 ;
  • R 2 or R 3 H, ⁇ CH 3 ,
  • R 4 a sugar ring (glucose ring, galactose ring, mannose ring and other polyhydroxy compounds conforming to the sugar definition);
  • R 5 H, ⁇ CH 3 ;
  • R 6 or R 7 H, ⁇ CH 3 ,
  • Step 1 dissolving the sugar-containing polymer in water to obtain a sugar-containing polymer photoresist solution
  • the step may be specifically carried out by dissolving the sugar-containing polymer in water to prepare a sugar-containing polymer photoresist solution having a concentration of from 0.1 mg/L to 100 g/L.
  • Step 2 depositing the photoresist solution on the surface of the substrate to be processed to form an electron beam photoresist film
  • the step may be performed by depositing the photoresist solution on the surface of the substrate to be processed to form an electron beam photoresist film, wherein the photoresist solution is deposited on the substrate to be processed.
  • the surface method is any one of a spin coating method and a drop coating method
  • the substrate is any one of a silicon wafer, an ITO glass, a quartz sheet having a gold film plating layer on the surface, and a SiO 2 sheet having a silver film plating layer on its surface. .
  • Step 4 Place it under a wavelength source of 300-800 nm wavelength range, which has a fluorescent effect.
  • the step may be specifically performed as follows: the sugar-containing polymer film forms carbon nano-dots at the exposure point, and the carbon nano-dots of a specific size have a corresponding quantum fluorescence effect, under the excitation of the corresponding wavelength ultraviolet or visible light , producing fluorescence.
  • FIG. 2 is an AFM characterization diagram of a carbon nano-dot photoresist pattern having a fluorescent effect according to the present invention.
  • FIG. 2 an enlarged scan of the exposed region can be found.
  • the surface contains dense nano-sized lattices (carbon dots).
  • Figure 3 is a precise map of the carbon nanodots with fluorescence effect of the present invention (SEM image and 405 nm excitation) Under the optical map).
  • a Au point (coated with a sugar film, the same below) SEM photograph
  • b optical image of Au point (405 nm excitation, dark color)
  • c SEM of the sugar-containing polymer carbon spot positioned at the lower right corner of the Au point Photograph
  • d Optical image of the sugar-containing polymer carbon spot positioned at the lower right corner of the Au spot (excitation at 405 nm, bright color at the lower right corner).
  • FIG. 3c is a block array fluorescence confocal diagram based on a sugar-containing polymer carbon dot of the present invention, and an ultraviolet absorption spectrum thereof and a fluorescence emission spectrum thereof.
  • a Confocal fluorescence pattern excited by 405nm wavelength light (this picture is not developed by ion water in the past, the gray point is the blue fluorescent area, which is the electron beam exposure area, and the rest is not exposed by electron beam)
  • b The ultraviolet absorption spectrum of the sugar polymer carbon dots (c line) and the fluorescence emission spectrum (d line 405 nm excitation), as shown in Fig. 4, the sample was placed in an ultraviolet-visible absorption spectrometer for testing, and the ultraviolet absorption of the film was obtained.
  • Spectrogram (c-line) we found a strong UV absorption peak at 360 nm.
  • an embodiment or “an embodiment” as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention.
  • Film formation and preparation method of carbon nano-dot photoresist with fluorescence effect preparing poly(acrylamide-based) glucose polymer aqueous solution (PAGA) with a mass ratio of 1:100 as a water-soluble negative electron beam photoresist,
  • PAGA poly(acrylamide-based) glucose polymer aqueous solution
  • the photoresist was spin-coated on the surface of the silicon wafer at a speed of 2000 rpm to a film thickness of about 40 nm. Then, it was exposed by electron beam, and the working voltage was 20 kV, the working distance was 10 mm, the aperture was 15 ⁇ m, and the exposure measurement was 2000 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm. Under a confocal microscope, excitation with 400 nm wavelength light, the exposed region has blue fluorescence.
  • the substrate was fully immersed in deionized water to develop an image with a single dot resolution of ⁇ 50 nm. Under a confocal microscope, it was excited with a light of 360 nm wavelength and developed with a fluorescent pattern.
  • Film formation and preparation method of carbon nano-dot photoresist with fluorescence effect preparing (methacrylamide-based) glucose and sodium p-styrenesulfonate copolymer (P(MAG-co-SS)) aqueous solution, mass ratio It is 1:100,000, as a water-soluble negative electron beam photoresist, which is applied onto the surface of the silicon wafer to quickly dry the water, and the film thickness is about 80 nm. Then, it was exposed by an electron beam, and the working voltage was 30 kV, the working distance was 10 mm, the aperture was 5 ⁇ m, and the exposure was measured at 1000 ⁇ C/cm 2 .
  • P(MAG-co-SS) sodium p-styrenesulfonate copolymer
  • the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • excitation with a light of 390 nm wavelength the exposed area has blue fluorescence.
  • Film formation and preparation method of carbon nano-dot photoresist with fluorescence effect preparing (methacrylamide-based) mannose (PMAM) aqueous solution with a mass ratio of 1:10000 as a water-soluble negative electron beam photoresist,
  • the photoresist was spin-coated at a speed of 2000 rpm on a quartz surface with a gold film to a film thickness of about 20 nm.
  • the working voltage was 20 kV
  • the working distance was 10 mm
  • the aperture was 30 ⁇ m
  • the exposure measurement was 20000 ⁇ C/cm 2 .
  • the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm. Under a confocal microscope, excitation with 380 nm wavelength light, the exposed region has blue fluorescence.
  • the present invention discloses a carbon nano-dot photoresist having a fluorescent effect and an image forming method thereof, which is a novel photosensitive resin based on a sugar-containing polymer and an electron beam etching technique to generate fluorescent carbon nano-dots in situ and
  • the photosensitive resin is a sugar-containing polymer, and its carbonized nano-point preparation with nanometer-scale precise positioning is realized by controlled carbonization and self-crosslinking in a certain electron beam exposure dose range.
  • Fluorescent properties under wavelength illumination for fluorescence development and other applications. Water is the only solvent used in this patent. It has the characteristics of green environmental protection, and can form fluorescent carbon nano-dots with arbitrary nano patterns at any specified position.
  • One step is to solve the problems of fluorescent particle preparation and nano-scale precise positioning in semiconductor manufacturing. And the biological field has broad application prospects.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une photorésine à nanopoints de carbone ayant un effet fluorescent, et son procédé d'imagerie, la résine photosensible étant un polymère contenant du sucre, son effet réglable de carbonisation et d'auto-réticulation dans une certaine plage de dose d'exposition de faisceau d'électrons étant utilisé pour préparer des nanopoints de carbone ayant un positionnement de précision nanométrique, et ses propriétés fluorescentes sous éclairage de longueurs d'onde spécifiques étant utilisées pour mettre en œuvre un développement de fluorescence et d'autres applications. L'eau est le seul solvant utilisé, ce qui rend l'invention respectueuse de l'environnement, et des nanopoints de carbone fluorescents ayant n'importe quel nanomotif peuvent être formés à n'importe quelle position spécifiée, résolvant les deux problèmes de préparation de particules fluorescentes et de positionnement de précision de nanoéchelle, et ayant une large portée destinée à une application dans la fabrication de semi-conducteurs et le champ biologique.
PCT/CN2017/109454 2017-04-27 2017-11-06 Photorésine à nanopoints de carbone à effet fluorescent, et son procédé d'imagerie Ceased WO2018196319A1 (fr)

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CN201710288631.1A CN107065436B (zh) 2017-04-27 2017-04-27 具有荧光效应的碳纳米点光刻胶及其成像方法
CN201710288631.1 2017-04-27

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106959584A (zh) * 2017-04-27 2017-07-18 苏州大学 水溶性负性电子束光刻胶及其成像方法
CN107065436B (zh) * 2017-04-27 2020-02-21 苏州大学 具有荧光效应的碳纳米点光刻胶及其成像方法
CN109749738B (zh) * 2017-11-01 2021-08-17 浙江糖能科技有限公司 磺化碳量子点、其制备方法以及作为催化剂在制备5-羟甲基糠醛中的应用
CN113376968B (zh) 2020-03-10 2023-04-07 长鑫存储技术有限公司 一种检测半导体制作工艺缺陷的方法
CN113444201A (zh) * 2021-06-29 2021-09-28 苏州大学 荧光含糖聚合物及其制备方法
KR20230022751A (ko) 2021-08-09 2023-02-16 삼성전자주식회사 전자 빔 노광 장치, 포토레지스트 검사 장치 및 이를 이용한 포토레지스트의 검사 방법
CN114111603B (zh) * 2021-11-26 2022-09-23 南京大学 一种器件微区工艺测量和校正方法
CN115826365A (zh) * 2022-12-23 2023-03-21 南京工业大学 一种通过全水基电子束曝光技术制备聚合物发光微纳结构的方法

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CN102713755A (zh) * 2009-08-26 2012-10-03 康宁股份有限公司 水凝胶成图与细胞培养制品
CN106959584A (zh) * 2017-04-27 2017-07-18 苏州大学 水溶性负性电子束光刻胶及其成像方法
CN107065436A (zh) * 2017-04-27 2017-08-18 苏州大学 具有荧光效应的碳纳米点光刻胶及其成像方法

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CN102713755A (zh) * 2009-08-26 2012-10-03 康宁股份有限公司 水凝胶成图与细胞培养制品
CN101799625A (zh) * 2009-12-18 2010-08-11 湛江师范学院 超支化聚酯微光学光刻胶
CN106959584A (zh) * 2017-04-27 2017-07-18 苏州大学 水溶性负性电子束光刻胶及其成像方法
CN107065436A (zh) * 2017-04-27 2017-08-18 苏州大学 具有荧光效应的碳纳米点光刻胶及其成像方法

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