WO2006095705A1 - Procede de formation de modele - Google Patents

Procede de formation de modele Download PDF

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Publication number
WO2006095705A1
WO2006095705A1 PCT/JP2006/304313 JP2006304313W WO2006095705A1 WO 2006095705 A1 WO2006095705 A1 WO 2006095705A1 JP 2006304313 W JP2006304313 W JP 2006304313W WO 2006095705 A1 WO2006095705 A1 WO 2006095705A1
Authority
WO
WIPO (PCT)
Prior art keywords
ring
photosensitive composition
light
compound
formula
Prior art date
Application number
PCT/JP2006/304313
Other languages
English (en)
Japanese (ja)
Inventor
Takashi Ubukata
Koji Takahashi
Yasushi Yokoyama
Original Assignee
National University Corporation Yokohama National University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National University Corporation Yokohama National University filed Critical National University Corporation Yokohama National University
Priority to JP2007507109A priority Critical patent/JPWO2006095705A1/ja
Publication of WO2006095705A1 publication Critical patent/WO2006095705A1/fr

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Classifications

    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H2001/026—Recording materials or recording processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/50—Reactivity or recording processes
    • G03H2260/52—Photochromic reactivity wherein light induces a reversible transformation between two states having different absorption spectra

Definitions

  • the present invention relates to a pattern forming method using a photosensitive composition, and in particular, a pattern using a photosensitive composition capable of forming a pattern only by light irradiation without performing a development step. It relates to the formation method.
  • the present inventors form a film using a composition containing a polymer compound having an azobenzene sensitive to light in the side chain and a liquid crystal molecule, and the film is irradiated with interference light to form a film.
  • a technique for forming a relief grating (diffraction grating) is reported (see, for example, Patent Document 1 and Non-patent Document 1). According to this technique, since the film of the light irradiation part is transferred, it is possible to form a regular pattern only by light irradiation without passing through the development step.
  • Patent Document 1 Patent 3451319
  • Non-Patent Document 1 Yasushi Yokoyama, Shun Hikaru, "New Photochromic Systems and Applications of Photochromism", Future Materials, Inc. 'N' T's, 2004, 4th, 6th, p. 28-34 Disclosure of the invention
  • an object of the present invention is to provide a pattern formation method using a novel photosensitive composition capable of forming a pattern without development by light irradiation.
  • the photosensitive composition is irradiated with light containing both the ring-opening wavelength light for ring-opening and the ring-closing wavelength light for ring-closing to cause mass transfer of the photosensitive composition.
  • the photosensitive composition after pattern formation has absorption in the ultraviolet and visible region, it is preferable to irradiate light for reducing the absorption out of the ring-opening wavelength light or the ring-closing wavelength light.
  • the photosensitive composition used in the present invention includes a photochromic compound which has a ring which is reversibly ring-closed by light and exhibits photochromism, and a polymer compound which becomes a matrix.
  • Photochromism refers to the reversible conversion of a single chemical species between two stable states by light.
  • an operating temperature indicating photochromism for example, room temperature can be mentioned.
  • R is a substituent such as, for example, CH or N.
  • photochromic compounds having a ring of Formula II include
  • R CH, CH, CH, R;
  • the UV light causes a ring opening reaction to the left and right to proceed, and the visible light reversibly causes a ring closure to the right and the left.
  • a cyclization reaction from left to right proceeds by UV light, and reversibly ring opening to the right by left light occurs by visible light.
  • the thermal stability depends on the structure of the compound.
  • the polymer compound serving as the matrix holds a predetermined shape of the photosensitive composition and serves as a binding agent when the composition is coated or the like.
  • a known matrix can be used.
  • polyalkyl methacrylates, polyalkyl acrylates, polystyrenes, amorphous polyolefins, polyaryl alkylals and the like can be used.
  • a photosensitive composition can be obtained by mixing these matrices with the above-mentioned photochromic compound and further appropriately blending predetermined solvents, additives and the like.
  • the blending amount of the matrix is preferably as small as possible, and usually, the matrix is blended at about 20 parts by mass of LOO to 100 parts by mass of the photochromic compound.
  • the photochromic compound may be polymerized to form a polymer photochromic compound.
  • the skeleton of the polymeric photochromic compound include polyalkyl atalylate, polyalkyl methacrylate, polyester, polyamide, polybutyl alcohol and the like.
  • radical polymerization, polycondensation, high molecular reaction and the like can be mentioned.
  • liquid crystal it is preferable to add a liquid crystal to the photosensitive composition used in the present invention because the photosensitive time can be greatly shortened.
  • the liquid crystal include 4-Sinano 4'-pentyl biphenyl, 4-Sinano 4 ', 1-heptyl biphenyl, 4-Sinano 4' pentyloxy biphenyl, 4-Siano 4'-heptyl oxybiphenyl And N- (4-methoxybenzylidene) 4 butylaline which can be used as a nematic liquid crystal at the pattern formation temperature (eg room temperature to 60 ° C.) is not.
  • the pattern formation temperature eg room temperature to 60 ° C.
  • the compounding ratio of these liquid crystal molecules to the photosensitive composition is not particularly limited, for example, it is preferable to set the liquid crystal ratio to the photochromic compound to be 0.3 to 0.6.
  • the liquid crystal ratio refers to the mass ratio of the liquid crystal to the photochromic compound.
  • the photosensitive composition can form a coating film by, for example, coating using spin coating, and the composition of the dark part other than the irradiated part can be formed by irradiating light at a predetermined position of the coating film.
  • a substance is moved to the bright part and gathered, or the composition of the irradiated part is moved so as to escape to the dark part or the like, thereby causing a pattern transfer.
  • the mass transfer due to light irradiation depends on the type and structure of the photochromic compound.
  • a ridge is provided at the light irradiation portion, and when the photosensitive composition escapes from the light irradiation portion, a groove is formed in the light irradiation portion.
  • the photosensitive composition in the irradiated part or the dark part can be moved by mass transfer to form a pattern.
  • the compound of the above-mentioned formula III it is irradiated with light including both UV light for ring opening and visible light for ring closing.
  • the irradiation light can be irradiated, for example, through a photomask of a predetermined pattern.
  • UV light also induces a ring closure reaction which is reduced only by the ring opening, so that the formation of asperities occurs even with pattern exposure of only ultraviolet light, and the following bombing effect can be induced. Therefore, light of a single wavelength can also be used as long as it is capable of simultaneously inducing ring opening and ring closing reaction.
  • the reason for irradiating both the ring-opening wavelength light and the ring-closing wavelength light is not clear, but is considered as follows. That is, in order to transfer the photosensitive composition in the irradiated part, the photochromic compound in the photosensitive composition repeats the ring-opening and 1-ring closure many times to change its conformation and make the whole composition flow by the bombing effect. It is thought that it is necessary. Therefore, even if only one of the ring-opening wavelength light and the ring-closing wavelength light is irradiated to advance either the ring-opening or ring-closing reaction, the mass transfer is not sufficiently performed! /.
  • photochromic compounds used in the present invention are stable and colorless, and are suitable, for example, for optical applications.
  • the photosensitive composition after formation of notches has absorption in the visible region, it may be irradiated with light for reducing the absorption out of ring-opening wavelength light or ring-closing wavelength light.
  • the ring-opened compound (the compound on the right side of the formula 3) has a purple color.
  • the photochromic compound in the photosensitive composition contains the ring-opening compound and the ring-closing compound at a constant ratio. For this reason, the photosensitive composition after noting formation will exhibit purple (it has an absorption spectrum in the ultraviolet visible region).
  • a photochromic compound exhibits photochromism, if the ring-opened compound is changed to a ring-closed compound (the compound on the left side of Chemical formula 3) after pattern formation, the compound becomes colorless and does not absorb in the visible region. . Therefore, by irradiating visible light to the whole photosensitive composition after pattern formation, it changes to a ring-closing compound, and a photosensitive composition can be made transparent.
  • mass transfer occurs when the photochromic compound repeats ring-opening and ring-closing many times, so that the formed pattern does not return to its original state even when irradiated with only ring-closing wavelength light.
  • the action to reduce the UV-visible absorption spectrum of the photosensitive composition after the pattern formation described above is unique to the photosensitive composition of the present invention.
  • the azovencene is changed to a cis-trans isomer which can not be opened by ring-closing ring closure by light, and the V-isomer is also absorbed in the UV-visible region, No action is obtained.
  • the above-mentioned visible absorption is reduced after pattern formation using the photosensitive composition of the present invention, it is suitably applicable to, for example, a wavelength programmable organic DFB (distributed feedback type) laser element.
  • a wavelength programmable organic DFB distributed feedback type
  • the present invention is not limited to the above embodiment.
  • the irradiation light in addition to a photomask, interference exposure can also be used.
  • the photosensitive composition of the present invention can be applied to light switching materials because the physical properties are greatly changed by light.
  • the photosensitive composition of the present invention since it does not require development and can form a fine pattern by dry operation by light irradiation, it can be used, for example, as a diffraction layer of a wavelength programmable DFB laser which can be set on the user side.
  • the photosensitive composition of the present invention is also applicable as a hologram material and a high density optical recording material.
  • the photosensitive composition of the present invention is mass-transferred as a whole by light irradiation, it can also be applied as a carrier (conveyance) of an object to which substance transfer is desired.
  • the photosensitive composition may be burnt out by firing or the like after irradiation with light.
  • a photochromic compound (spiropyran derivative) exhibiting photochromism as shown in the following, using polymethylmetatalylate (PMMA) as a matrix, 2.5 mass% of a spiropyran derivative in a solvent (cloform), and PMMA 1.7.
  • the photosensitive composition was manufactured by adding% by mass.
  • the above-mentioned spiropyran derivative opens when irradiated with UV light near 350 nm, and closes when irradiated with visible light near 550 nm.
  • the ring-opened compound has a purple color
  • the ring-closed compound is colorless and transparent.
  • the photosensitive composition was spin-coated on a flat glass substrate, and the solvent was evaporated to prepare a thin film having a thickness of 640 nm.
  • a light mask with a line width of 6.25 m in the light transmission area and a space width of 150 m is attached closely to the above film, and the light source power of a super high pressure mercury lamp is taken out by a long pass filter. 2 ) I was irradiated for 2 hours.
  • the shape of the obtained pattern was measured by an atomic force microscope. The measurement results are shown in Fig.1.
  • the entire surface of the patterned photosensitive composition was irradiated with visible light having a wavelength of 540 nm or more (intensity: 0.06 WZ cm 2 ), and only the ring closure reaction of the compound of formula IX was allowed to proceed.
  • the purple color (absorption wavelength 550 nm) of the photosensitive composition turned to be colorless and transparent, and the light absorption at a wavelength of 350 to 650 nm was reduced.
  • a photochromic compound shown in Table 1 was blended with PMMA to prepare a photosensitive composition, and a pattern of ridge structures was formed in the same manner as in Example 1, and height differences of the ridges were measured.
  • Example 2 a plurality of lattice masks constituting a repetitive pattern of light and dark with a period of 8 m were used as a photomask.
  • Samples 2 to 4 and Samples 5 to 7 in Table 1 have different molecular weights of substituents (linear alkyl groups) in the same complex. From these results, it was found that the height difference of the ridge becomes higher as the straight chain alkyl group which is a substituent is longer.
  • the compound of the formula IX (spiropyran derivative) used in Example 1 is incorporated as a photochromic compound in a dye concentration of 60% by mass, and 40% by mass of PMMA as a high molecular compound is incorporated, and 4-cyano-4, -pentylbiphenyl is further incorporated as a liquid crystal molecule.
  • Liquid crystal ratio Mass ratio of liquid crystal to spiropyran derivative
  • the composition was spin coated on a flat glass substrate and the solvent was evaporated to form a thin film.
  • Photomasks with multiple grating masks that make up an 8 ⁇ m periodic pattern of light and dark The above thin film was subjected to mask exposure (light source, wavelength) for a predetermined time to form a concavo-convex pattern.
  • the photosensitive composition was prepared by diluting to a polymer concentration of 1.11% by mass. The composition was spin coated on a flat glass substrate and the solvent was evaporated to form a thin film.
  • the thin film was subjected to mask exposure (light source, wavelength) for 20 minutes to form a concavo-convex pattern.
  • the height difference of the ridges of this pattern was about 100 nm.
  • the thin film after forming the concavo-convex pattern was heated on a hot plate at 56 to 58 ° C. for 30 minutes to eliminate the concavo-convex pattern. After disappearance, the thin film became almost flat.
  • FIG. 1 It is a figure which shows the shape of the pattern obtained by light-irradiating to a photosensitive composition.
  • FIG. 2 is a view showing an absorption spectrum of the photosensitive composition before and after the patterned photosensitive composition is irradiated with visible light that causes only a ring closure reaction to proceed.

Abstract

L’invention concerne un procédé de formation d’un modèle utilisant une nouvelle composition photosensible capable de transférer un modèle par irradiation lumineuse sans subir de développement. L’invention prévoit une composition photosensible comprenant un composé photochromique, ayant un cycle capable de s’ouvrir et de se fermer de manière réversible en présence de lumière et/ou de chaleur afin de faire preuve de photochromisme, et un composé polymère en tant que matrice, le cycle ayant la structure répondant à la formule (I) : (R1 et R2 représentent des substituants et peuvent former un cycle et R3 représente un substituant) ou à la formule (II) : (R4 et R5 représentent des substituants). Cette composition est irradiée par des rayons contenant un rayon d’une longueur d’onde d'ouverture de cycle capable d’ouvrir le cycle et un rayon d’une longueur d’onde de fermeture de cycle capable de fermer le cycle de façon à effectuer un transfert de masse de la composition photosensible.
PCT/JP2006/304313 2005-03-09 2006-03-07 Procede de formation de modele WO2006095705A1 (fr)

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Application Number Priority Date Filing Date Title
JP2007507109A JPWO2006095705A1 (ja) 2005-03-09 2006-03-07 パターン形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005065616 2005-03-09
JP2005-065616 2005-03-09

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WO2006095705A1 true WO2006095705A1 (fr) 2006-09-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007031649A (ja) * 2005-07-29 2007-02-08 Japan Atomic Energy Agency 量子ビーム照射と光照射又は加熱により可逆的に着色／脱色する有機分子を含んだ樹脂組成物とナノパターン形成方法
JP2011237508A (ja) * 2010-05-07 2011-11-24 Yokohama National Univ パターン形成方法
WO2020228176A1 (fr) * 2019-05-16 2020-11-19 深圳市华星光电技术有限公司 Matrice noire, procédé de préparation associé, et panneau d'affichage

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61123835A (ja) * 1984-11-20 1986-06-11 Unitika Ltd 感光性樹脂組成物
JPH0419749A (ja) * 1990-05-15 1992-01-23 Mitsubishi Electric Corp パターン形成方法
JPH04107545A (ja) * 1990-08-28 1992-04-09 Sharp Corp 光メモリー素子の製造方法
JP2002105339A (ja) * 2000-09-28 2002-04-10 Tokyo Inst Of Technol 感光性組成物、感光性薄膜、及びパターン形成方法
JP2003073381A (ja) * 2001-08-31 2003-03-12 Fuji Photo Film Co Ltd 光学活性フルギド化合物
JP2003082033A (ja) * 2001-09-17 2003-03-19 Rikogaku Shinkokai 光表面レリーフ形成用感光性材料および感光性薄膜、並びにその感光性材料を用いたレリーフ形成方法
JP2004079121A (ja) * 2002-08-21 2004-03-11 Mitsubishi Chemicals Corp 光学的情報記録方法及び光学的情報記録装置
JP2004093658A (ja) * 2002-08-29 2004-03-25 Toshiba Corp 情報記録媒体および情報記録装置
JP2004258224A (ja) * 2003-02-25 2004-09-16 Asahi Denka Kogyo Kk 光記録媒体
JP2005109329A (ja) * 2003-10-01 2005-04-21 Institute Of Physical & Chemical Research 発振波長可変の有機分布帰還型レーザ
JP2005301202A (ja) * 2004-03-19 2005-10-27 Fuji Xerox Co Ltd ホログラム記録媒体およびこれを用いたホログラム記録方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61123835A (ja) * 1984-11-20 1986-06-11 Unitika Ltd 感光性樹脂組成物
JPH0419749A (ja) * 1990-05-15 1992-01-23 Mitsubishi Electric Corp パターン形成方法
JPH04107545A (ja) * 1990-08-28 1992-04-09 Sharp Corp 光メモリー素子の製造方法
JP2002105339A (ja) * 2000-09-28 2002-04-10 Tokyo Inst Of Technol 感光性組成物、感光性薄膜、及びパターン形成方法
JP2003073381A (ja) * 2001-08-31 2003-03-12 Fuji Photo Film Co Ltd 光学活性フルギド化合物
JP2003082033A (ja) * 2001-09-17 2003-03-19 Rikogaku Shinkokai 光表面レリーフ形成用感光性材料および感光性薄膜、並びにその感光性材料を用いたレリーフ形成方法
JP2004079121A (ja) * 2002-08-21 2004-03-11 Mitsubishi Chemicals Corp 光学的情報記録方法及び光学的情報記録装置
JP2004093658A (ja) * 2002-08-29 2004-03-25 Toshiba Corp 情報記録媒体および情報記録装置
JP2004258224A (ja) * 2003-02-25 2004-09-16 Asahi Denka Kogyo Kk 光記録媒体
JP2005109329A (ja) * 2003-10-01 2005-04-21 Institute Of Physical & Chemical Research 発振波長可変の有機分布帰還型レーザ
JP2005301202A (ja) * 2004-03-19 2005-10-27 Fuji Xerox Co Ltd ホログラム記録媒体およびこれを用いたホログラム記録方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007031649A (ja) * 2005-07-29 2007-02-08 Japan Atomic Energy Agency 量子ビーム照射と光照射又は加熱により可逆的に着色／脱色する有機分子を含んだ樹脂組成物とナノパターン形成方法
JP2011237508A (ja) * 2010-05-07 2011-11-24 Yokohama National Univ パターン形成方法
WO2020228176A1 (fr) * 2019-05-16 2020-11-19 深圳市华星光电技术有限公司 Matrice noire, procédé de préparation associé, et panneau d'affichage

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