WO2014088189A1 - Method for forming flattened film comprising uv curable organosiloxane resin, and flattened film formed thereby - Google Patents

Method for forming flattened film comprising uv curable organosiloxane resin, and flattened film formed thereby Download PDF

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WO2014088189A1
WO2014088189A1 PCT/KR2013/007689 KR2013007689W WO2014088189A1 WO 2014088189 A1 WO2014088189 A1 WO 2014088189A1 KR 2013007689 W KR2013007689 W KR 2013007689W WO 2014088189 A1 WO2014088189 A1 WO 2014088189A1
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organosiloxane resin
forming
resin layer
gate
weight
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PCT/KR2013/007689
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French (fr)
Korean (ko)
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송부섭
손인영
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삼성정밀화학 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • H01L29/78636—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device with supplementary region or layer for improving the flatness of the device
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT

Definitions

  • the present invention relates to a method of forming a planarization film including an ultraviolet curable organosiloxane resin, and a planarization film formed therefrom, and more particularly, to an optical device such as a liquid crystal display (LCD) or an organic electroluminescent display (OLED).
  • the present invention relates to a method for forming a planarization film including an ultraviolet curable organosiloxane resin, and a planarization film formed therefrom.
  • the resistance of the wiring material is decreasing.
  • a silicon nitride (SiNx) or silicon oxide (SiO 2 ) thin film is formed by a vacuum CVD method, but as shown in FIG. 1, a gate 20 having a thickness of 0.3 ⁇ m or less is formed on the substrate 10.
  • the gate insulating film 30 is properly formed, but when the thick gate 20 of 1 ⁇ m or more is applied, an electrical short circuit occurs because the gate insulating film 30 is not formed in a cross section or is formed very thin. There has been a problem that it is difficult to form another thin film layer such as a semiconductor layer to be formed on the upper layer.
  • planarization film 40 is formed using a solution-type organic material or an inorganic and organic-inorganic hybrid material on the substrate 10 on which the thick gate 20 having a thickness of 1 ⁇ m or more is inevitably formed.
  • a step with the gate top was generated so that an additional planarization process was necessarily accompanied.
  • the planarization film must have high adhesion to the substrate or lower layer to be formed, and also the layer formed on the planarization film, and effectively prevent the compound contained in the material from interfering with each other and causing adverse effects.
  • the diffusion of copper wiring material used as the gate metal wiring should be prevented and the oxide film should be effectively prevented from forming and the influence of the gate insulating film or semiconductor material formed on the planarization film should be minimized.
  • planarization film itself should be very transparent and free from deterioration such as yellowing or whitening for a long time under exposure to high temperature, high humidity, and ultraviolet rays.
  • the present invention hydrolyzes and polymerizes silane, which is not an organic composition composed of a carbon compound, which is conventionally used, and then uses a siloxane oligomer having a photosensitive function as a flattening film forming material, and coats the flattening film material in a downward direction.
  • silane which is not an organic composition composed of a carbon compound, which is conventionally used
  • a siloxane oligomer having a photosensitive function as a flattening film forming material
  • the problem to be solved by the present invention is to provide a method of forming a planarization film including an ultraviolet curable organosiloxane resin.
  • Another object of the present invention is to provide a planarization film including an ultraviolet curable organosiloxane resin.
  • the present invention comprises the steps of forming an ultraviolet curable organosiloxane resin layer on a substrate formed with an ultraviolet gate; Irradiating ultraviolet rays toward the lower side of the substrate to form a cured organosiloxane resin layer, wherein the cured organosiloxane resin layer is left on the gate so as not to be exposed to ultraviolet light; Removing the organosiloxane resin layer that is not cured with a developer; And it provides a method of forming a planarization film comprising the step of etching the organosiloxane resin layer cured with a developer.
  • the ultraviolet curable organosiloxane resin layer is preferably formed by coating a gate thickness or more, and the amount of ultraviolet light is preferably 50 to 300mJ / cm 2.
  • the ultraviolet curable organosiloxane resin includes a photosensitive organosiloxane oligomer having a polystyrene reduced weight average molecular weight of 100 to 100,000.
  • the photosensitive organosiloxane oligomer is synthesized by hydrolyzing and polymerizing silane to prepare a siloxane oligomer, and then adding a photosensitive function to the siloxane oligomer.
  • silane phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tetramethoxysilane and tetra It is preferable that at least one selected from the group consisting of methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, and methacrylate propyltri as a compound for adding the photosensitive function.
  • methoxysilane or glycidyloxypropyltri methoxysilane is selected.
  • the UV-curable organosiloxane resin is 40 to 70% by weight of the photosensitive organic siloxane oligomer; 10 to 40% by weight of the organic solvent; 5 to 20% by weight of a polyfunctional (meth) acrylic monomer; 3 to 15% by weight photoinitiator; And 0.1 to 2.0 wt% leveling agent.
  • the gate preferably has a thickness of 1 ⁇ m or more.
  • the method of forming the gate planarization film according to the present invention it is preferable to further include the step of aging for 15 minutes to 1 hour at 150 to 250 °C to have a surface hardness of 5H or more after the etching.
  • the present invention provides a gate planarization film including an ultraviolet curable organosiloxane resin containing a photosensitive organosiloxane oligomer formed according to the gate planarization film forming method.
  • the thickness step by using the thick metal wiring can be preferably flattened.
  • the planarization film obtained therefrom is excellent in surface hardness and transparent.
  • FIG. 1 is a cross-sectional view showing a gate and insulating film structure of a conventional TFT.
  • FIG. 2 is a cross-sectional view showing a structure in which a solution planarization film is formed in a gate and insulating film structure of a conventional TFT.
  • Figure 3 is a schematic diagram showing a planarization film forming process according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram illustrating a process of forming a gate insulating film after the planarization film is formed in the TFT according to the exemplary embodiment of the present invention.
  • FIG. 5 is a schematic diagram illustrating a process of forming a planarization film after forming a gate insulating film in a TFT according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram showing a planarization film forming process according to an embodiment of the present invention.
  • the present invention provides a method of forming an ultraviolet curable organosiloxane resin layer on a substrate on which an ultraviolet gate is formed (S11); Irradiating ultraviolet rays toward the lower side of the substrate surface to form a cured organosiloxane resin layer, but leaving the uncured organosiloxane resin layer not to be exposed to ultraviolet light on the gate (S12); Removing the organosiloxane resin layer that is not cured with the developer (S13); And it provides a method of forming a gate planarization film comprising the step (S14) of etching the organosiloxane resin layer cured with a developer.
  • the gate 200 is first formed on the substrate 100 to 1 ⁇ m or more, and then the gate 200 is formed.
  • An ultraviolet curable organosiloxane resin layer 300 is formed on the formed substrate 100.
  • the substrate 100 may be one that is generally used in this field, for example, a glass substrate, a plastic substrate and the like may be used.
  • the gate 200 may be formed of a metal having a thickness of 1 ⁇ m or more so as to realize low resistance of the metal wiring, preferably copper.
  • the resin layer 300 is for flattening the thickness step when a gate having a thickness of 1 ⁇ m or more is used, and the resin layer 300 is formed using an ultraviolet curable organosiloxane resin containing a photosensitive organosiloxane oligomer. It is preferable.
  • combines a siloxane oligomer by hydrolyzing-polymerizing a silane, and then synthesize
  • the photosensitive organosiloxane oligomer preferably has a polystyrene reduced weight average molecular weight of 100 to 100,000, and if it is out of the above range, that is, less than 100, the molecular weight is too small to form a durable coating, difficult to form a gel when 100,000 or more As a homogeneous and stable solution, it is difficult to store and to form a uniform coating film.
  • Silanes used to synthesize the photosensitive organosiloxane oligomers include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane.
  • Tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane can be selected one or more selected from the group consisting of, but is not limited thereto. .
  • a photosensitive group is provided to the siloxane oligomer synthesize
  • Methacrylate propyl trimethoxysilane, glycidyloxy propyl trimethoxysilane, etc. can be used as an alicyclic compound for providing the said photosensitive group, However, It is not limited to this.
  • the ultraviolet curable organosiloxane resin includes an organic solvent, a polyfunctional (meth) acrylic monomer, a photoinitiator, a leveling agent, and the like, in addition to the photosensitive organic siloxane oligomer, as described above.
  • the UV-curable organosiloxane resin included in the gate planarization film according to the present invention includes 40 to 70% by weight of the photosensitive organosiloxane oligomer; 10 to 40% by weight of the organic solvent; 5 to 20% by weight of a multifunctional (meth) acrylic monomer; 3 to 15% by weight photoinitiator; And 0.1 to 2% by weight of a surface conditioner (leveling agent).
  • the organic solvent may be methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, 2-butanol, 1-pentanol, 3-methylbutanol, 2-methylbutanol, 2-pentanol, 4-methyl- Alcohols such as 2-pentanol, cyclohexanol, methylcyclohexanol, n-hexanol, perfuryl alcohol, perfuryl methanol, tetrahydrofurfuryl alcohol and benzyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclo Ketones such as pentanone,
  • the type and amount of solvent are appropriately selected depending on the application conditions and the drying conditions when forming the membrane structure. It is preferable that the composition contains a concentration of 15 to 45% by weight of solids to facilitate the drying and baking process of the solvent carried out during the formation of the membrane structure, and to improve the properties of the finally obtained membrane structure.
  • a solvent can be used individually or in mixture of 2 or more types, It is preferable to use the solvent which has a boiling point of 100 degrees C or less, and the solvent (boiling solvent) which has a boiling point of 120-160 degreeC.
  • the high boiling solvent prevents voids by volatilizing at a lower temperature than the temperature at which the coating, drying, and curing are performed when forming the membrane structure, and serves to improve the flatness of the membrane structure by slow drying the film.
  • a solvent selected from the group consisting of ethanol, 2-propanol and 2-butanol and a group selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and n-propyl acetate The solvent used can be mixed and used.
  • (meth) acrylate As a polyfunctional (meth) acrylate, (meth) acrylate more than bifunctional group is preferable, As a bifunctional (meth) acrylate, ethylene glycol (meth) acrylate and 1, 6- hexanediol (meth) are mentioned, for example. ) Acrylate, 1, 9-nonanediol (meth) acrylate, propylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.
  • (meth) acrylate more than trifunctional for example, tris hydroxyethyl isocyanurate, tri (meth) acrylate, a trimethol propane tri (meth) acrylate, pentaerythritol tri (meth) acryl
  • the rate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
  • photoinitiators photopolymerization initiators and photosensitizers known in the art may be used, and 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4 '-Methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3', 4'-dimethoxyphenyl Triazine compounds such as) -6-triazine and 3- ⁇ 4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio ⁇ propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazo
  • a leveling agent for example, a group consisting of polyether-modified polymethylalkylsiloxane, polyester-modified polymethylalkylsiloxane, acrylate copolymer, polyacrylate solution It may be used alone or in combination of two or more, but is not limited thereto.
  • the formed resin layer 300 is dried to remove the solvent.
  • the drying process may vary depending on the organic solvent used, but may be dried by heating at 90 to 120 ° C. for 1 to 30 minutes.
  • the gate 200 becomes a mask so that an uncured resin layer 301 remains on the upper portion of the gate, and the remaining portion becomes a resin layer 302 cured by ultraviolet rays.
  • the ultraviolet rays may be irradiated within a range that is general in the art, for example, 50 to 300 mJ / cm 2, preferably at a light amount of 100 to 200 mJ / cm 2.
  • the amount of ultraviolet light is less than 50, hardening may not be performed properly, thereby deteriorating physical properties, and when irradiated in excess of 300, energy may be excessively consumed in the process.
  • the step S13 of removing the uncured resin layer 301 with the developer and the step S14 of etching the cured resin layer 302 at a constant speed with the developer occur simultaneously or sequentially. Only the uncured resin layer 301 is removed, and after the development is completed, the cured resin layer 302 is etched and flattened to a constant thickness.
  • the developing solution used may be a basic aqueous solution such as TMAH, KOH, NaOH, but is not limited thereto.
  • the etching rate may vary depending on the properties of the material, but is, for example, 0.2 ⁇ m / minute to 1.2 ⁇ m / minute.
  • the flattening film may further include the step of aging for 15 minutes to 1 hour at 150 to 250 °C to have a surface hardness of 5H or more pencil hardness.
  • the planarization film formed by the formation method as described above may have excellent surface hardness and transparency, and may planarize the thickness step generated by using a thick metal wiring to realize low resistance of the metal wiring.
  • the planarization film may form the gate insulating film 400 after forming the resin layer 300 used as the planarization film. Also, the planarization film may be formed before the resin layer 300 is formed. 400).
  • 159 parts by weight of phenyltrimethoxysilane, 143 parts by weight of methyltriethoxysilane and 167 parts by weight of tetraethoxysilane were placed in a flask of about 2 liters equipped with a cooling tube and a stirrer.
  • the solution which mixed the concentration of nitric acid and 136 weight part of purified water was slowly dripped using the dropping funnel installed in the flask.
  • an exothermic reaction occurred in the flask contents, and initially a white cloudy solution, but stirring continued to give a colorless transparent solution.
  • the temperature of the solution synthesized as described above was cooled to 50 ° C. or lower, and refluxed under normal pressure for 3 hours to cool to room temperature.
  • the solution which mixed 233.5 weight part of methacrylate propyl trimethoxysilane and 5.3 weight part of glycidyloxypropyl trimethoxysilane was dripped slowly at the normal temperature using the dropping funnel installed in the flask. This colorless transparent solution was heated to normal reflux for 2 hours to obtain a photosensitive organosiloxane oligomer a.
  • the additives were mixed in a ratio of Table 1, aged at 4 ° C. for 12 hours, and then filtered through a 0.2 ⁇ m PTFE (polytetrafluoroethylene) filter to prepare a composition A.
  • TMPTA Trimethylolpropane triacrylate
  • Irgacure 369 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone
  • the composition A was spin-coated on a glass substrate having a 2 ⁇ m thick copper wire and dried at 120 ° C. for 1 minute to form a 3 ⁇ m thick coating film.
  • the glass substrate coated with the composition was irradiated with ultraviolet light at a light quantity of 100 mJ / cm 2 to the glass substrate surface in the downward direction using an ultraviolet exposure machine (MA6, SUSS Micro Co., Ltd.) to cure only the exposed flattened portion without exposing the upper portion of the copper conductor. Was made.
  • the cured coating was then developed in a 2.38% solution of tetramethyl ammonium hydroxide (TMAH) at 30 ° C.
  • TMAH tetramethyl ammonium hydroxide
  • the composition A was spin-coated on a glass substrate having a 2 ⁇ m thick copper wire and dried at 120 ° C. for 1 minute to form a 3 ⁇ m thick coating film.
  • the glass substrate coated with the composition was irradiated with ultraviolet light at a light quantity of 200 mJ / cm 2 to the glass substrate surface in the downward direction by using an ultraviolet exposure machine (MA6, SUSS Micro Co., Ltd.), thereby curing only the exposed flattened portion without exposing the upper portion of the copper conductor. Was made.
  • the cured coating film was developed in a TMAH 2.38% solution at 30 ° C.

Abstract

The present invention relates to a method for forming a flattened film comprising a UV curable organosiloxane resin, and a flattened film formed thereby. The method for forming a flattened film according to the present invention comprises the steps of: forming a UV curable organosiloxane resin layer on a substrate having a gate formed therewith;forming a cured organosiloxane resin layer by irradiating UV rays in a lower direction of a substrate surface so as to prevent an upper portion of the gate from being exposed to UV rays such that an uncured organosiloxane resin layer remains; removing the uncured organosiloxane resin layer by using a developer; and etching the cured organosiloxane resin layer by using a developer. The method for forming a flattened film according to the present invention can preferably remove a thickness difference due to a use of a thick metal wire, which is used to implement low resistance of a metal wire for developing a super high-resolution ultrafast TFT.

Description

자외선 경화형 유기실록산 수지를 포함한 평탄화막의 형성방법 및 이로부터 형성된 평탄화막Method for Forming Flattening Film Including UV Curable Organosiloxane Resin And Flattening Film Formed Therefrom
본 발명은 자외선 경화형 유기실록산 수지를 포함한 평탄화막의 형성방법 및 이로부터 형성된 평탄화막에 관한 것으로, 보다 상세하게는 액정 표시 소자(LCD)나 유기 전계발광 표시장치(OLED) 등의 광 장치에 사용되는 자외선 경화형 유기실록산 수지를 포함한 평탄화막의 형성방법 및 이로부터 형성된 평탄화막에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a planarization film including an ultraviolet curable organosiloxane resin, and a planarization film formed therefrom, and more particularly, to an optical device such as a liquid crystal display (LCD) or an organic electroluminescent display (OLED). The present invention relates to a method for forming a planarization film including an ultraviolet curable organosiloxane resin, and a planarization film formed therefrom.
화면이 대형화되고 3D 디스플레이와 같이 응답속도의 고속화를 위해서는 배선재료의 저항은 낮아지는 추세이다.In order to increase the screen size and speed up the response speed like the 3D display, the resistance of the wiring material is decreasing.
이에 따라 게이트 금속배선으로 두꺼운 구리배선 재료를 사용함으로써 저저항을 실현하여 대형화, 고해상도의 초고속 TFT를 개발하려는 노력이 전개되고 있다. 특히 게이트 금속배선으로 1㎛ 이상의 두꺼운 구리배선을 채용코자 노력하고 있다.As a result, efforts are being made to develop ultra-high-speed TFTs of large size and high resolution by realizing low resistance by using a thick copper wiring material as the gate metal wiring. In particular, efforts have been made to employ thick copper wiring of 1 탆 or more as the gate metal wiring.
두꺼운 구리배선이 사용됨에 따라 게이트의 두께 차이를 극복할 수 있는 평탄화 기술이 요구되고 있으며, 구체적으로 다양한 크기의 배선을 균일하게 평탄화할 수 있는 성능의 재료와 형성방법의 개발이 요구되고 있다.As thick copper wires are used, a planarization technology for overcoming the difference in gate thickness is required, and in particular, development of a material and a formation method capable of uniformly planarizing wires of various sizes is required.
종래의 게이트 절연막은 실리콘 나이트라이드(SiNx) 또는 실리콘 옥사이드(SiO2) 박막을 진공상의 CVD 방법으로 형성하였으나, 도 1에서 보여지는 바와 같이 기판(10)상에 0.3㎛ 이하의 게이트(20)을 형성하는 경우, 게이트 절연막(30)이 제대로 형성되고 있지만, 1㎛ 이상의 두꺼운 게이트(20)를 적용할 경우 단면부에 게이트 절연막(30)이 형성되지 않거나 매우 얇게 형성됨에 따라 전기적 단락 현상이 발생하고 상부층에 형성되어야 할 반도체층 등의 다른 박막층을 성형시키기 어려워지는 문제가 있었다. In the conventional gate insulating film, a silicon nitride (SiNx) or silicon oxide (SiO 2 ) thin film is formed by a vacuum CVD method, but as shown in FIG. 1, a gate 20 having a thickness of 0.3 μm or less is formed on the substrate 10. In the case of forming, the gate insulating film 30 is properly formed, but when the thick gate 20 of 1 μm or more is applied, an electrical short circuit occurs because the gate insulating film 30 is not formed in a cross section or is formed very thin. There has been a problem that it is difficult to form another thin film layer such as a semiconductor layer to be formed on the upper layer.
또한 도 2에 나타난 바와 같이 1㎛ 이상의 두꺼운 게이트(20)가 형성된 기판(10) 상에 용액형의 유기재료 또는 무기 및 유무기 하이브리드 재료를 사용하여 평탄화막(40)을 형성할 경우에도 필연적으로 게이트 상부와의 단차가 발생되어 추가적인 평탄화 공정이 필수적으로도 동반되어야 한다는 문제가 있었다.Also, as shown in FIG. 2, even when the planarization film 40 is formed using a solution-type organic material or an inorganic and organic-inorganic hybrid material on the substrate 10 on which the thick gate 20 having a thickness of 1 μm or more is inevitably formed. There was a problem in that a step with the gate top was generated so that an additional planarization process was necessarily accompanied.
이러한 평탄화막은 형성되는 기판 또는 하층, 또한 평탄화막 상부에 형성되는 층과 부착력이 높아야 하며 재료에 포함되어 있는 화합물이 층간 확산되어 나쁜 영향을 끼치는 것을 효과적으로 차단하여야 한다.The planarization film must have high adhesion to the substrate or lower layer to be formed, and also the layer formed on the planarization film, and effectively prevent the compound contained in the material from interfering with each other and causing adverse effects.
특히 게이트 금속배선으로 사용되는 구리배선 재료의 확산을 방지하고 산화막이 형성되는 것을 효과적으로 차단하여야 하며 평탄화막 상부에 형성되는 게이트 절연막 또는 반도체 재료와의 영향도 최소화되어야 한다In particular, the diffusion of copper wiring material used as the gate metal wiring should be prevented and the oxide film should be effectively prevented from forming and the influence of the gate insulating film or semiconductor material formed on the planarization film should be minimized.
또한, 평탄화막 자체는 매우 투명하고 고온, 고습 및 자외선 등의 노출에 대해 장시간 황변이나 백화 등의 변질이 없어야 한다. In addition, the planarization film itself should be very transparent and free from deterioration such as yellowing or whitening for a long time under exposure to high temperature, high humidity, and ultraviolet rays.
이에 본 발명은 종래에 사용하고 있는 탄소화합물로 구성된 유기계 조성물이 아닌 실란을 가수분해 중합하고, 이어 감광성 기능을 부가시킨 실록산 올리고머를 평탄화막 형성 재료로 사용하고, 이 평탄화막 재료를 코팅하여 하부 방향인 기재면 쪽으로 자외선을 조사하여 경화하는 경우, 두꺼운 금속 배선을 적용한 바람직한 평탄화막을 구현할 수 있어, 고해상도의 초고속 TFT를 개발할 수 있음을 밝힌 것이다.Accordingly, the present invention hydrolyzes and polymerizes silane, which is not an organic composition composed of a carbon compound, which is conventionally used, and then uses a siloxane oligomer having a photosensitive function as a flattening film forming material, and coats the flattening film material in a downward direction. When irradiated with ultraviolet rays toward the surface of the phosphor substrate, the planarization film to which a thick metal wiring is applied can be realized, and thus a high-speed TFT of high resolution can be developed.
본 발명이 해결하고자 하는 과제는 자외선 경화형 유기실록산 수지를 포함한 평탄화막의 형성방법을 제공하는 것이다.The problem to be solved by the present invention is to provide a method of forming a planarization film including an ultraviolet curable organosiloxane resin.
본 발명이 해결하고자 하는 또 다른 과제는 자외선 경화형 유기실록산 수지를 포함하는 평탄화막을 제공하는 것이다. Another object of the present invention is to provide a planarization film including an ultraviolet curable organosiloxane resin.
상기 과제를 해결하기 위해, 본 발명은 자외선 게이트가 형성된 기판 상에 자외선 경화형 유기실록산 수지층을 형성하는 단계; 상기 기판면의 하부방향으로 자외선을 조사하여, 경화 유기실록산 수지층을 형성하되, 게이트 상부에는 자외선에 노출되지 않게 하여 경화되지 않은 유기실록산 수지층이 남도록 하는 단계; 현상액으로 경화되지 않는 유기실록산 수지층을 제거하는 단계; 및 현상액으로 경화된 유기실록산 수지층을 식각하는 단계를 포함하는 평탄화막의 형성방법을 제공한다.In order to solve the above problems, the present invention comprises the steps of forming an ultraviolet curable organosiloxane resin layer on a substrate formed with an ultraviolet gate; Irradiating ultraviolet rays toward the lower side of the substrate to form a cured organosiloxane resin layer, wherein the cured organosiloxane resin layer is left on the gate so as not to be exposed to ultraviolet light; Removing the organosiloxane resin layer that is not cured with a developer; And it provides a method of forming a planarization film comprising the step of etching the organosiloxane resin layer cured with a developer.
본 발명에 따른 게이트 평탄화막의 형성방법에서, 상기 자외선 경화형 유기실록산 수지층은 게이트 두께 이상으로 코팅하여 형성하는 것이 바람직하며, 상기 자외선의 광량은 50 내지 300mJ/㎠인 것이 바람직하다.In the method for forming a gate planarization film according to the present invention, the ultraviolet curable organosiloxane resin layer is preferably formed by coating a gate thickness or more, and the amount of ultraviolet light is preferably 50 to 300mJ / cm 2.
본 발명에 따른 게이트 평탄화막의 형성방법에서, 상기 자외선 경화형 유기실록산 수지는 폴리스티렌 환산 중량 평균분자량이 100 내지 100,000인 감광성 유기 실록산 올리고머를 포함한다. 또한, 상기 감광성 유기 실록산 올리고머는 실란을 가수분해 중합시켜 실록산 올리고머를 제조하고, 이어서 상기 실록산 올리고머에 감광성 기능을 부가하여 합성한 것이다.In the method for forming a gate planarization film according to the present invention, the ultraviolet curable organosiloxane resin includes a photosensitive organosiloxane oligomer having a polystyrene reduced weight average molecular weight of 100 to 100,000. In addition, the photosensitive organosiloxane oligomer is synthesized by hydrolyzing and polymerizing silane to prepare a siloxane oligomer, and then adding a photosensitive function to the siloxane oligomer.
여기서, 상기 실란으로는 페닐트리메톡시실란, 페닐트리에톡시실란, 디페닐트리메톡시실란, 디페닐에톡시실란, 메틸트리에톡시실란, 메틸트리메톡시실란, 테트라메톡시실란, 테트라에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 디메틸디메톡시실란 및 디메틸디에톡시실란으로 이루어진 군에서 일종 이상 선택되는 것이 바람직하고, 상기 감광성 기능을 부가하기 위한 화합물로 메타아크릴레이트프로필트리메톡시실란 또는 글리시딜옥시프로필트리 메톡시실란이 선택되는 것이 바람직하다.Here, as the silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tetramethoxysilane and tetra It is preferable that at least one selected from the group consisting of methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane, and methacrylate propyltri as a compound for adding the photosensitive function. Preferably, methoxysilane or glycidyloxypropyltri methoxysilane is selected.
본 발명에 따른 게이트 평탄화막의 형성방법에서, 상기 자외선 경화형 유기실록산 수지는 감광성 유기 실록산 올리고머 40 내지 70중량%; 유기 용매 10 내지 40중량%; 다관능기 (메타)아크릴 모노머 5내지 20중량%; 광개시제 3 내지 15중량%; 및 레벨링제 0.1 내지 2.0중량%를 포함한다.In the method of forming a gate planarization film according to the present invention, the UV-curable organosiloxane resin is 40 to 70% by weight of the photosensitive organic siloxane oligomer; 10 to 40% by weight of the organic solvent; 5 to 20% by weight of a polyfunctional (meth) acrylic monomer; 3 to 15% by weight photoinitiator; And 0.1 to 2.0 wt% leveling agent.
또한, 상기 게이트는 통상 1㎛ 이상의 두께를 갖는 것이 바람직하다.In addition, the gate preferably has a thickness of 1 μm or more.
아울러, 본 발명에 따른 게이트 평탄화막의 형성방법에서, 상기 식각하는 단계 후에, 연필경도 5H 이상의 표면경도를 갖도록 150 내지 250℃에서 15분 내지 1시간 동안 숙성하는 단계를 더 포함하는 것이 바람직하다.In addition, in the method of forming the gate planarization film according to the present invention, it is preferable to further include the step of aging for 15 minutes to 1 hour at 150 to 250 ℃ to have a surface hardness of 5H or more after the etching.
상기 또 다른 과제를 해결하기 위해, 본 발명은 상기 게이트 평탄화막 형성방법에 따라 형성된 감광성 유기 실록산 올리고머를 포함하는 자외선 경화형 유기실록산 수지를 포함하는 게이트 평탄화막을 제공한다.In order to solve the above another problem, the present invention provides a gate planarization film including an ultraviolet curable organosiloxane resin containing a photosensitive organosiloxane oligomer formed according to the gate planarization film forming method.
본 발명에 따른 자외선 경화형 유기실록산 수지를 포함한 평탄화막의 형성방법은 대형화, 고해상도의 초고속 TFT 개발을 위한 금속배선의 저저항을 실현하고자 두꺼운 금속배선을 사용함에 따른 두께 단차를 바람직하게 평탄화할 수 있다. 또한, 이로부터 얻은 평탄화막은 표면경도가 우수하며 투명하다.In the method of forming the planarization film including the ultraviolet curable organosiloxane resin according to the present invention, in order to realize a large resistance and low resistance of the metal wiring for the development of ultra-high speed TFT of high resolution, the thickness step by using the thick metal wiring can be preferably flattened. In addition, the planarization film obtained therefrom is excellent in surface hardness and transparent.
도 1은 종래 TFT의 게이트 및 절연막 구조를 나타낸 단면도이다.1 is a cross-sectional view showing a gate and insulating film structure of a conventional TFT.
도 2는 종래 TFT의 게이트 및 절연막 구조에서 용액형 평탄화막이 형성된 구조를 나타낸 단면도이다.2 is a cross-sectional view showing a structure in which a solution planarization film is formed in a gate and insulating film structure of a conventional TFT.
도 3은 본 발명의 일구현예에 따른 평탄화막 형성과정을 나타낸 모식도이다.Figure 3 is a schematic diagram showing a planarization film forming process according to an embodiment of the present invention.
도 4는 본 발명의 일 구현예에 따른 TFT에서 평탄화막 형성후 게이트 절연막을 형성하는 과정을 나타낸 모식도이다.4 is a schematic diagram illustrating a process of forming a gate insulating film after the planarization film is formed in the TFT according to the exemplary embodiment of the present invention.
도 5는 본 발명의 일 구현예에 따른 TFT에서 게이트 절연막 형성후 평탄화막을 형성하는 과정을 나타낸 모식도이다.FIG. 5 is a schematic diagram illustrating a process of forming a planarization film after forming a gate insulating film in a TFT according to an embodiment of the present invention.
이하, 본 발명은 도면을 참조하여 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to the drawings.
도 3은 본 발명의 일구현예에 따른 평탄화막 형성과정을 나타낸 모식도이다. Figure 3 is a schematic diagram showing a planarization film forming process according to an embodiment of the present invention.
도 3을 참조하면, 본 발명은 자외선 게이트가 형성된 기판 상에 자외선 경화형 유기실록산 수지층을 형성하는 단계(S11); 상기 기판면의 하부방향으로 자외선을 조사하여, 경화 유기실록산 수지층을 형성하되, 게이트 상부에는 자외선에 노출되지 않게 하여 경화되지 않은 유기실록산 수지층이 남도록 하는 단계(S12); 현상액으로 경화되지 않는 유기실록산 수지층을 제거하는 단계(S13); 및 현상액으로 경화된 유기실록산 수지층을 식각하는 단계(S14)를 포함하는 게이트 평탄화막의 형성방법을 제공한다.Referring to FIG. 3, the present invention provides a method of forming an ultraviolet curable organosiloxane resin layer on a substrate on which an ultraviolet gate is formed (S11); Irradiating ultraviolet rays toward the lower side of the substrate surface to form a cured organosiloxane resin layer, but leaving the uncured organosiloxane resin layer not to be exposed to ultraviolet light on the gate (S12); Removing the organosiloxane resin layer that is not cured with the developer (S13); And it provides a method of forming a gate planarization film comprising the step (S14) of etching the organosiloxane resin layer cured with a developer.
상기 자외선 게이트가 형성된 기판 상에 자외선 경화형 유기실록산 수지층을 형성하는 단계(S11)에서, 우선적으로 기판(100) 상에 게이트(200)를 1㎛ 이상으로 형성시키고, 이어서, 게이트(200)가 형성된 기판(100) 상에 자외선 경화형 유기실록산 수지층(300)을 형성시킨다.In the step (S11) of forming an ultraviolet curable organosiloxane resin layer on the substrate on which the ultraviolet gate is formed, the gate 200 is first formed on the substrate 100 to 1 μm or more, and then the gate 200 is formed. An ultraviolet curable organosiloxane resin layer 300 is formed on the formed substrate 100.
여기서, 기판(100)으로 이 분야에 일반적으로 사용되는 것이 사용될 수 있으며, 예를 들면 유리기판, 플라스틱 기판 등등이 사용될 수 있다.Here, the substrate 100 may be one that is generally used in this field, for example, a glass substrate, a plastic substrate and the like may be used.
또한, 게이트(200)로는 금속배선의 저저항을 실현할 수 있도록 1㎛ 이상의 두께로 금속이 형성될 수 있으며, 바람직하게는 구리이다.In addition, the gate 200 may be formed of a metal having a thickness of 1 μm or more so as to realize low resistance of the metal wiring, preferably copper.
상기 수지층(300)은 1㎛ 이상의 두께를 갖는 게이트가 사용되는 경우 두께 단차를 평탄화하기 위한 것이며, 상기 수지층(300)은 감광성 유기 실록산 올리고머를 포함하는 자외선 경화형 유기실록산 수지를 사용하여 형성되는 것이 바람직하다.The resin layer 300 is for flattening the thickness step when a gate having a thickness of 1 μm or more is used, and the resin layer 300 is formed using an ultraviolet curable organosiloxane resin containing a photosensitive organosiloxane oligomer. It is preferable.
여기서, 상기 감광성 유기 실록산 올리고머는 실란을 가수분해 중합시켜 실록산 올리고머를 합성하고, 이어서 상기 실록산 올리고머에 감광성 기능을 부가하여 합성시킨 것이다.Here, the said photosensitive organosiloxane oligomer synthesize | combines a siloxane oligomer by hydrolyzing-polymerizing a silane, and then synthesize | combining by adding a photosensitive function to the said siloxane oligomer.
이 경우, 상기 감광성 유기 실록산 올리고머는 폴리스티렌 환산 중량 평균분자량이 100 내지 100,000인 것이 바람직하여, 상기 범위를 벗어나는 경우, 즉, 100이하인 경우 분자량이 너무 작아 내구성 있는 도막 형성이 어렵고, 100,000 이상인 경우 겔 형성으로 균일하고 안정한 용액으로 보관이 어렵고 균일한 도막을 형성하기 어렵다In this case, the photosensitive organosiloxane oligomer preferably has a polystyrene reduced weight average molecular weight of 100 to 100,000, and if it is out of the above range, that is, less than 100, the molecular weight is too small to form a durable coating, difficult to form a gel when 100,000 or more As a homogeneous and stable solution, it is difficult to store and to form a uniform coating film.
상기 감광성 유기 실록산 올리고머를 합성하기 위해 사용되는 실란으로는 페닐트리메톡시실란, 페닐트리에톡시실란, 디페닐트리메톡시실란, 디페닐에톡시실란, 메틸트리에톡시실란, 메틸트리메톡시실란, 테트라메톡시실란, 테트라에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 디메틸디메톡시실란 및 디메틸디에톡시실란으로 이루어진 군에서 일종 이상 선택되어 사용될 수 있지만, 이것으로 제한되는 것은 아니다.Silanes used to synthesize the photosensitive organosiloxane oligomers include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, and methyltrimethoxysilane. , Tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane can be selected one or more selected from the group consisting of, but is not limited thereto. .
또한, 감광성 기능을 부가하기 위하여, 실란을 가수분해 중합시켜 합성한 실록산 올리고머에 감광성기를 부여한다. 상기 감광성기를 부여하기 위환 화합물로는 메타아크릴레이트프로필트리메톡시실란 또는 글리시딜옥시프로필트리메톡시실란 등을 사용할 수 있지만, 이것으로 제한되는 것은 아니다.Moreover, in order to add photosensitive function, a photosensitive group is provided to the siloxane oligomer synthesize | combined by hydrolyzing-polymerizing a silane. Methacrylate propyl trimethoxysilane, glycidyloxy propyl trimethoxysilane, etc. can be used as an alicyclic compound for providing the said photosensitive group, However, It is not limited to this.
상기 자외선 경화형 유기실록산 수지에는 위에서 설명된 바와 같이 감광성 유기 실록산 올리고머 이외에 유기용매, 다관능기 (메타)아크릴 모노머, 광개시제 및 레벨링제 등이 포함된다. The ultraviolet curable organosiloxane resin includes an organic solvent, a polyfunctional (meth) acrylic monomer, a photoinitiator, a leveling agent, and the like, in addition to the photosensitive organic siloxane oligomer, as described above.
구체적으로 본 발명에 따른 게이트 평탄화막에 포함되는 상기 자외선 경화형 유기실록산 수지는 감광성 유기 실록산 올리고머 40 내지 70중량%; 유기 용매 10 내지 40중량%; 다관능기 (메타)아크릴 모노머 5 내지 20중량%; 광개시제 3 내지 15중량%; 및 표면조절제(레벨링제) 0.1 내지 2중량%를 포함한다.Specifically, the UV-curable organosiloxane resin included in the gate planarization film according to the present invention includes 40 to 70% by weight of the photosensitive organosiloxane oligomer; 10 to 40% by weight of the organic solvent; 5 to 20% by weight of a multifunctional (meth) acrylic monomer; 3 to 15% by weight photoinitiator; And 0.1 to 2% by weight of a surface conditioner (leveling agent).
여기서, 유기용매로는 메탄올, 에탄올, 2-프로판올, 1-프로판올, 1-부탄올, 2-부탄올, 1-펜타놀, 3-메틸부탄올, 2-메틸부탄올, 2-펜타놀, 4-메틸-2-펜타놀, 사이클로헥사놀, 메틸사이클로헥사놀, n-헥사놀, 퍼퓨릴알코올, 퍼퓨릴메탄올, 테트라하이드로퍼퓨릴알콜, 벤질알콜 등의 알코올류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메틸n-부틸케톤, 메틸t-부틸케톤, 메틸n-펜틸케톤, 메틸n-헥실케톤, 디에틸케톤, 디이소프로필케톤, 디이소부틸케톤, 시클로펜타논, 시클로헥사논, 메틸시클로헥사논, 시클로헵타논, 시클로옥타논, 2,4-펜타네디온, 2,5-헥사디온, 아세토페논 등의 케톤류; n-펜탄, 이소펜탄, n-헥산, 이소헥산, n-헵탄, 이소헵탄, 옥탄, 이소옥탄, 2,2,4-트리에틸펜탄, 시클로헥산, 메틸시클로헥산, 벤젠, 톨루엔, 자일렌, 트리에틸벤젠, 에틸벤젠, 메틸에틸벤젠, n-프로필벤젠, 이소프로필벤젠, 펜틸벤젠, 디에틸벤젠, 이소부틸벤젠, 트리에틸벤젠, 디이소프로필벤젠 등의 하이드로카본류; 테트라하이드로퓨란, 2-메틸테트라하이드로퓨란, 디에틸에테르, 디-n-프로필에테르, 디-이소프로필에테르, 디-n-부틸에테르, 디-이소부틸에테르, 디-n-헥실에테르, 아니솔, 페네톨, 디페닐에테르, 에틸벤질에테르, bis(2-에틸헥실)에테르, 에틸렌옥사이드, 1,2-프로필렌옥사이드, 1,4-디옥산, 4-메틸디옥솔레인, 디메틸디옥솔레인, 디벤질에테르, 부틸페닐에테르 등 에테르류; 메틸아세테이트, 에틸아세테이트, n-프로필아세테이트, 이소프로필아세테이트, n-부틸아세테이트, 이소부틸아세테이트, sec-부틸아세테이트, n-펜틸아세테이트, sec-펜틸아세테이트, 메틸펜틸아세테이트, 2-에틸부틸아세테이트, 2-에틸헥실아세테이트, 벤질아세테이트, 시클로헥실아세테이트, 메틸시클로헥실아세테이트, n-노닐아세테이트, 메틸아세토아세테이트, 에틸아세토아세테이트, 에틸프로피오네이트, n-부틸프로피오네이트, 이소아밀프로피오네이트, 메틸피루베이트, 에틸피루베이트, 디에틸옥살레이트, 디-n-부틸옥살레이트, 메틸락테이트, 에틸락테이트, 부틸락테이트, n-펜틸락테이트, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트, 디에틸말로네이트, 디메틸프탈레이트, 디에틸프탈레이트, 디에틸카보네이트, 프로필렌카보네이트 등의 에스테르류; 감마-부티롤락톤, 감마-발레롤락톤, 델타-발레롤락톤 등의 락톤류; 아세토니트릴, 프로피오노니트릴, 아크릴로니트릴 등 니트릴류; 에틸렌글리콜, 프로필렌글리콜, 1,2-부타네디올, 1,3-부타네디올, 1,2-펜탄세디올, 2,4-펜탄디올, 2-메틸펜탄-2,4-디올, 2,5-헥사네디올, 2,4-헵타네디올, 2-에틸헥산-1,3-디올, 디에틸렌글리콜, 디프로필렌글리콜, 트리에틸렌글리콜, 트리프로필렌글리콜 등 글리콜류; 하이드록시아세톤(아세톨), 3-하이드록시-3-메틸-2-부타논, 4-하이드록시-3-메틸-2-부타논, 5-하이드록시-2-펜타논, 4-하이드록시-4-메틸-2-펜타논 등의 하이드록시케톤류; 글리콜에테르류로서, 에틸렌글로콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노n-부틸에테르, 에틸렌글리콜모노n-펜틸에테르, 에틸렌글리콜모노n-헥실에테르, 에틸렌글리콜모노2-에틸부틸에테르, 에틸렌글리콜모노2-에틸헥실에테르, 에틸렌글리콜모노페닐에테르 등의 에틸렌글리콜모노에테르류; 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜메틸에틸에테르, 에틸렌글리콜디부틸에테르 등의 에틸렌글리콜디에테르류; 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜모노프로필에테르아세테이트, 에틸렌글리콜모노n-부틸에테르아세테이트, 에틸렌글리콜디아세테이트 등의 에틸렌글리콜아세테이트류; 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노n-프로필에테르, 프로필렌글리콜모노n-부틸에테르, 프로필렌글리콜모노t-부틸에테르 등의 프로필렌글리콜모노에테르류; 프로필렌글리콜디메틸에테르, 프로필렌글리콜디에틸에테르, 프로필렌글리콜메틸에틸에테르 등의 프로필렌글리콜디에테르류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노n-프로필에테르아세테이트, 프로필렌글리콜모노n-부틸에테르아세테이트, 프로필렌글리콜디아세테이트 등의 프로필렌글리콜아세테이트류; 3-메톡시-1-부탄올, 3-메톡시부틸아세테이트, 3-메틸-3-메톡시-1-부탄올, 3-메톡시-1-부틸아세테이트, 3-메틸-3-메톡시-1-부틸아세테이트 등의 부틸렌글리콜유도체; 디에틸글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노프로필에테르, 디에틸렌글리콜모노n-부틸에테르, 디에틸렌글리콜모노n-헥실에테르 등의 디에틸글리콜모노에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르류, 디에틸렌글리콜디에틸에테르 등의 디에틸렌글리콜디에테르류; 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노프로필에테르아세테이트, 디에틸렌글리콜모노n-부틸에테르아세테이트 등의 디에틸렌글리콜아세테이트류; 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노프로필에테르 등의 디프로필렌글리콜모노에테르류; 디프로필렌글리콜디메틸에테르 등의 디프로필렌글리콜디에테르류; 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트 등의 글리콜에테르아세테이트류; 또는 불균질화합물로서, N-메틸피롤리디논, 포름아미드, N-메틸포름아미드, N-에틸포름아미드, N,N-디메틸포름아미드, N,N-디에틸포름아미드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N,N-디에틸아세트아미드, N-메틸프로피온아미드, N,N-디메틸술폭사이드, 술포레인, 1,3-프로페인설톤 등을 용매로 포함할 수 있다.The organic solvent may be methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, 2-butanol, 1-pentanol, 3-methylbutanol, 2-methylbutanol, 2-pentanol, 4-methyl- Alcohols such as 2-pentanol, cyclohexanol, methylcyclohexanol, n-hexanol, perfuryl alcohol, perfuryl methanol, tetrahydrofurfuryl alcohol and benzyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclo Ketones such as pentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2,4-pentanedione, 2,5-hexadione and acetophenone; n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, octane, isooctane, 2,2,4-triethylpentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, tri Hydrocarbons such as ethyl benzene, ethyl benzene, methyl ethyl benzene, n-propyl benzene, isopropyl benzene, pentyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene and diisopropyl benzene; Tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, di-isobutyl ether, di-n-hexyl ether, anisole , Phentol, diphenyl ether, ethyl benzyl ether, bis (2-ethylhexyl) ether, ethylene oxide, 1,2-propylene oxide, 1,4-dioxane, 4-methyldioxoleine, dimethyldioxolane, Ethers such as dibenzyl ether and butylphenyl ether; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2 Ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methylpyru Bate, ethylpyruvate, diethyl oxalate, di-n-butyloxalate, methyl lactate, ethyl lactate, butyl lactate, n-pentyl lactate, methyl methoxy propionate, ethyl ethoxy propionate , Diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate, propylene carbonate The esters; Lactones such as gamma-butyrolactone, gamma-valerolactone and delta-valerolactone; Nitriles such as acetonitrile, propiononitrile and acrylonitrile; Ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanecediol, 2,4-pentanediol, 2-methylpentane-2,4-diol, 2, Glycols such as 5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; Hydroxyacetone (acetol), 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy Hydroxy ketones such as -4-methyl-2-pentanone; As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono n-hexyl ether, ethylene Ethylene glycol monoethers such as glycol mono2-ethylbutyl ether, ethylene glycol mono2-ethylhexyl ether, and ethylene glycol monophenyl ether; Ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dibutyl ether; Ethylene glycol acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol mono n-butyl ether acetate, and ethylene glycol diacetate; Propylene glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether and propylene glycol mono t-butyl ether; Propylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol methyl ethyl ether; Propylene glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate, and propylene glycol diacetate; 3-methoxy-1-butanol, 3-methoxybutylacetate, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methyl-3-methoxy-1- Butylene glycol derivatives, such as butyl acetate; Diethyl glycol monoethers such as diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono n-butyl ether and diethylene glycol mono n-hexyl ether; Diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, and diethylene glycol diethyl ether; Diethylene glycol acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol mono n-butyl ether acetate; Dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether; Dipropylene glycol diethers such as dipropylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether acetate; Or as a heterogeneous compound, N-methylpyrrolidinone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide , N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N, N-dimethylsulfoxide, sulfolane, 1,3-propanesultone and the like may be included as a solvent. have.
용매의 종류와 양은 막 구조물 형성시 도포 조건 및 건조 조건에 따라 적절히 선택하여 사용한다. 조성물에는 고형분의 농도가 15 내지 45중량%로 포함되게 하는 것이 막 구조물의 형성 과정에서 수행되는 용매의 건조 및 베이크 공정을 용이하게 하며, 최종적으로 얻어지는 막 구조물의 특성 향상에 유리하므로 바람직하다. The type and amount of solvent are appropriately selected depending on the application conditions and the drying conditions when forming the membrane structure. It is preferable that the composition contains a concentration of 15 to 45% by weight of solids to facilitate the drying and baking process of the solvent carried out during the formation of the membrane structure, and to improve the properties of the finally obtained membrane structure.
또한, 용매는 단독 또는 2종 이상을 혼합하여 사용할 수 있으며, 바람직하게는 100℃ 이하의 끓는점을 갖는 용매를 120 내지 160℃의 끓는점을 갖는 용매(고비등 용매)와 혼합하여 사용하는 것이 좋다. 상기 고비등 용매는 막 구조물 형성시 도포, 건조, 및 경화가 이루어지는 온도보다 좀 더 낮은 온도에서 휘발하여 보이드(Void)를 방지하며, 필름을 저속 건조시킴으로써 막 구조물의 평탄성을 향상시키는 역할을 한다. 이러한 용매의 조합으로서, 에탄올, 2-프로판올 및 2-부탄올로 이루어진 그룹에서 선택되는 용매와 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 메틸이소부틸케톤 및 n-프로필아세테이트로 이루어지는 그룹에서 선택되는 용매를 혼합하여 사용할 수 있다.In addition, a solvent can be used individually or in mixture of 2 or more types, It is preferable to use the solvent which has a boiling point of 100 degrees C or less, and the solvent (boiling solvent) which has a boiling point of 120-160 degreeC. The high boiling solvent prevents voids by volatilizing at a lower temperature than the temperature at which the coating, drying, and curing are performed when forming the membrane structure, and serves to improve the flatness of the membrane structure by slow drying the film. As a combination of these solvents, a solvent selected from the group consisting of ethanol, 2-propanol and 2-butanol and a group selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and n-propyl acetate The solvent used can be mixed and used.
다관능기 (메타)아크릴레이트로는 2관능기 이상의 (메타)아크릴레이트가 바람직하며, 2관능 (메타)아크릴레이트로는, 예를 들면 에틸렌글리콜 (메타)아크릴레이트, 1,6-헥산디올(메타)아크릴레이트, 1,9-노난디올 (메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 테트라에틸렌글리콜 (메타)아크릴레이트, 비스페녹시 에틸알콜 플루오렌 디아크릴레이트 등을 들 수 있다. 또한, 3관능 이상의 (메타)아크릴레이트로는, 예를 들면 트리스히드록시에틸이소시아누레이트, 트리(메타)아크릴레이트, 트리메티롤프로판 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트 등을 들 수 있다.As a polyfunctional (meth) acrylate, (meth) acrylate more than bifunctional group is preferable, As a bifunctional (meth) acrylate, ethylene glycol (meth) acrylate and 1, 6- hexanediol (meth) are mentioned, for example. ) Acrylate, 1, 9-nonanediol (meth) acrylate, propylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned. Moreover, as (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate, tri (meth) acrylate, a trimethol propane tri (meth) acrylate, pentaerythritol tri (meth) acryl The rate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
이러한 2관능 또는 3관능 이상의 (메타)아크릴레이트 중에서 선택하여 단독으로 또는 조합하여 사용할 수 있다.It can select from these bifunctional or trifunctional or more than (meth) acrylate, and can use individually or in combination.
광개시제로는 이 분야에 알려진 광중합 개시제 및 광증감제를 사용할 수 있으며, 2,4-트리클로로메틸-(4'-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(피플로닐)-6-트리아진, 2,4-트리클로로메틸-(3',4'-디메톡시페닐)-6-트리아진, 3-{4-[2,4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오} 프로판산 등의 트리아진 화합물; 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐 비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸 등의 비이미다졸 화합물; 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐 (2-히드록시)프로필 케톤, 1-히드록시시클로헥실 페닐 케톤, 벤조인메틸 에테르, 벤조인에틸 에테르, 벤조인이소부틸 에테르, 벤조인부틸 에테르, 2,2-디메톡시-2-페닐 아세토페논, 2-메틸-(4-메틸티오페닐)-2-몰폴리노-1-프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-몰포리노페닐)-1-부타논 등의 아세토페논계 화합물; 벤조페논, 4,4'-비스(디메틸아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 2,4,6-트리메틸아미노벤조페논, 메틸-o-벤조일벤조에이트, 3,3-디메틸-4-메톡시벤조페논, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논 등의 벤조페논계 화합물; 9-플로레논, 2-클로로-9-플로레논, 2-메틸-9-플로레논 등의 플로레논계 화합물; 티옥산톤, 2,4-디에틸 티옥산톤, 2-클로로 티옥산톤, 1-클로로-4-프로필옥시 티옥산톤, 이소프로필 티옥산톤, 디이소프로필 티옥산톤 등의 티옥산톤계 화합물; 크산톤, 2-메틸크산톤 등의 크산톤계 화합물; 안트라퀴논, 2-메틸 안트라퀴논, 2-에틸 안트라퀴논, t-부틸 안트라퀴논, 2,6-디클로로-9,10-안트라퀴논 등의 안트라퀴논계 화합물; 9-페닐아크리딘, 1,7-비스(9-아크리디닐)헵탄, 1,5-비스(9-아크리디닐)펜탄, 1,3-비스(9-아크리디닐)프로판 등의 아크리딘계 화합물; 벤질, 1,7,7-트리메틸-비스클로[2,2,1]헵탄-2,3-디온, 9,10-펜안트렌퀴논 등의 디카르보닐 화합물; 2,4,6-트리메틸벤조일 디페닐포스핀 옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸 포스핀 옥사이드, 비스(2,6-디클로로벤조일) 프로필 포스핀 옥사이드 등의 포스핀 옥사이드계 화합물; 메틸 4-(디메틸아미노)벤조에이트, 에틸-4-(디메틸아미노)벤조에이트, 2-n-부톡시에틸 4-(디메틸아미노)벤조에이트, 2,5-비스(4-디에틸아미노벤잘)시클로펜타논, 2,6-비스(4-디에틸아미노벤잘)시클로헥사논, 2,6-비스(4-디에틸아미노벤잘)-4-메틸-시클로헥사논 등의 아민계 시너지스트; 3,3'-카르보닐비닐-7-(디에틸아미노)쿠마린, 3-(2-벤조티아졸일)-7-(디에틸아미노)쿠마린, 3-벤조일-7-(디에틸아미노)쿠마린, 3-벤조일-7-메톡시-쿠마린,10,10'-카르보닐비스[1,1,7,7-테트라메틸-2,3,6,7-테트라하이드로-1H,5H,11H-Cl]-벤조피라노[6,7,8-ij]-퀴놀리진-11-온 등의 쿠마린계 화합물; 4-디에틸아미노 칼콘, 4-아지드벤잘아세토페논 등의 칼콘 화합물; 2-벤조일메틸렌, 3-메틸-β-나프토티아졸린 또는 이들의 혼합물이 있으며, 이것으로 제한되는 것은 아니다.As photoinitiators, photopolymerization initiators and photosensitizers known in the art may be used, and 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4 '-Methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3', 4'-dimethoxyphenyl Triazine compounds such as) -6-triazine and 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole compounds such as 5′-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzoinbutyl ether, 2,2-dimethoxy- 2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenone compounds such as -1-butanone; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3 Benzophenone compounds such as 3,3-dimethyl-4-methoxybenzophenone and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Fluorenone compounds such as 9- fluorenone, 2-chloro-9- fluorenone and 2-methyl-9- fluorenone; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bisclo [2,2,1] heptane-2,3-dione, 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; Methyl 4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine synergists such as cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] Coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene, 3-methyl-β-naphthothiazoline or mixtures thereof, but is not limited thereto.
또한, 레벨링제로는 표면조절제, 표면처리제, 코팅조절제 등이 사용되며, 예를 들면, 폴리에테르 변성 폴리메틸알킬실록산, 폴리에스테르변성 폴리메틸알킬실록산, 아크릴레이트 공중합체, 폴리아크릴레이트 용액으로 이루어지는 군으로부터 단독으로 또는 2종 이상 혼합 사용될 수 있지만, 이것으로 제한되는 것은 아니다.In addition, as a leveling agent, a surface control agent, a surface treatment agent, a coating control agent and the like are used, for example, a group consisting of polyether-modified polymethylalkylsiloxane, polyester-modified polymethylalkylsiloxane, acrylate copolymer, polyacrylate solution It may be used alone or in combination of two or more, but is not limited thereto.
상기 형성된 수지층(300)은 용매를 제거하기 위하여 건조 과정을 거친다. 이때 건조과정은 사용된 유기 용매에 따라 달라질 수 있지만, 90 내지 120℃에서 1분 내지 30분 동안 가열하는 것을 통해 건조될 수 있다.The formed resin layer 300 is dried to remove the solvent. The drying process may vary depending on the organic solvent used, but may be dried by heating at 90 to 120 ° C. for 1 to 30 minutes.
이어서, 상기 기판면의 하부방향으로 자외선을 조사하여, 경화 유기실록산 수지층(302)을 형성하되, 게이트 상부에는 자외선에 노출되지 않게 하여 경화되지 않은 유기실록산 수지층(301)이 남도록 하는 단계(S12)가 진행된다.Subsequently, ultraviolet rays are irradiated toward the lower side of the substrate surface to form a cured organosiloxane resin layer 302, but the uncured organosiloxane resin layer 301 remains on the gate so as not to be exposed to ultraviolet rays ( S12) proceeds.
이 경우, 별도의 마스크가 요구되지 않으며, 게이트(200)가 마스크가 되어 게이트 상부는 경화되지 않은 수지층(301)이 남게 되고, 나머지 부분은 자외선에 의해 경화된 수지층(302)이 된다.In this case, a separate mask is not required, and the gate 200 becomes a mask so that an uncured resin layer 301 remains on the upper portion of the gate, and the remaining portion becomes a resin layer 302 cured by ultraviolet rays.
이때, 자외선은 이 분야에 일반적인 범위 내에서 조사될 수 있으며, 예를 들면, 50 내지 300mJ/㎠이고, 바람직하게는 100 내지 200mJ/㎠의 광량으로 조사되는 것이다. 상기 자외선 광량이 50 미만인 경우, 경화가 제대로 되지 않아 물성이 나빠질 수 있으며, 300을 초과하여 조사되는 경우 공정상 에너지가 지나치게 소모될 수 있다.In this case, the ultraviolet rays may be irradiated within a range that is general in the art, for example, 50 to 300 mJ / cm 2, preferably at a light amount of 100 to 200 mJ / cm 2. When the amount of ultraviolet light is less than 50, hardening may not be performed properly, thereby deteriorating physical properties, and when irradiated in excess of 300, energy may be excessively consumed in the process.
상기 현상액으로 경화되지 않은 수지층(301)을 제거하는 단계(S13)와 현상액으로 일정한 속도로 경화된 수지층(302)을 식각하는 단계(S14)는 동시적으로 또는 순차적으로 일어나며, 현상 직후에는 경화되지 않은 수지층(301)만이 제거되고, 현상이 완료된 후에는 경화된 수지층(302)이 일정한 두께로 식각되어 평탄화된다. 이 경우, 사용되는 현상액으로는 TMAH, KOH, NaOH 등의 염기성 수용액 사용될 수 있으며, 이것으로 제한되는 것은 아니다. 상기 식각 속도는 재료에 특성에 따라 달라질 수 있지만, 예를 들면, 0.2㎛/분 내지 1.2㎛/분이다.The step S13 of removing the uncured resin layer 301 with the developer and the step S14 of etching the cured resin layer 302 at a constant speed with the developer occur simultaneously or sequentially. Only the uncured resin layer 301 is removed, and after the development is completed, the cured resin layer 302 is etched and flattened to a constant thickness. In this case, the developing solution used may be a basic aqueous solution such as TMAH, KOH, NaOH, but is not limited thereto. The etching rate may vary depending on the properties of the material, but is, for example, 0.2 μm / minute to 1.2 μm / minute.
본 발명에 따른 평탄화막의 형성방법에서, 상기 식각하는 단계 후에 상기 평탄화막이 연필경도 5H 이상의 표면경도를 갖도록 150 내지 250℃에서 15분 내지 1시간 동안 숙성하는 단계를 더 포함할 수 있다.In the method of forming a flattening film according to the present invention, after the etching step, the flattening film may further include the step of aging for 15 minutes to 1 hour at 150 to 250 ℃ to have a surface hardness of 5H or more pencil hardness.
상기와 같은 형성방법으로 형성된 평탄화막은 표면 경도가 우수하고 투명성을 가지며, 금속배선의 저저항을 실현하고자 두꺼운 금속배선을 사용함으로써 발생되는 두께 단차를 평탄화할 수 있다.The planarization film formed by the formation method as described above may have excellent surface hardness and transparency, and may planarize the thickness step generated by using a thick metal wiring to realize low resistance of the metal wiring.
상기 평탄화막은 도 4 및 도 5에 나타난 바와 같이, 평탄화막으로 사용되는 수지층(300)을 형성한 후 게이트 절연막(400)을 형성할 수도 있으며, 또한, 수지층(300) 형성 전에 게이트 절연막(400)을 형성할 수 있다.As shown in FIGS. 4 and 5, the planarization film may form the gate insulating film 400 after forming the resin layer 300 used as the planarization film. Also, the planarization film may be formed before the resin layer 300 is formed. 400).
이하, 본 발명은 실시예를 들어 더욱 상세히 설명하지만, 본 발명이 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.
합성예 1Synthesis Example 1
냉각관과 교반기가 구비된 약 2리터 용량의 플라스크에 페닐트리메톡시실란 159 중량부, 메틸트리에톡시실란 143 중량부 및 테트라에톡시실란 167 중량부를 넣고, 내용물을 격렬하게 교반하면서, 1 노르말 농도의 질산과 정제된 물 136 중량부를 혼합한 용액을 플라스크에 설치한 적하 깔때기를 이용하여 천천히 적하하였다. 그 결과, 플라스크 내용물에서는 발열반응이 일어났고, 초기에는 백색의 혼탁한 용액이었지만 교반을 지속한 결과 무색 투명한 용액이 되었다.159 parts by weight of phenyltrimethoxysilane, 143 parts by weight of methyltriethoxysilane and 167 parts by weight of tetraethoxysilane were placed in a flask of about 2 liters equipped with a cooling tube and a stirrer. The solution which mixed the concentration of nitric acid and 136 weight part of purified water was slowly dripped using the dropping funnel installed in the flask. As a result, an exothermic reaction occurred in the flask contents, and initially a white cloudy solution, but stirring continued to give a colorless transparent solution.
상기와 같이 합성된 용액의 온도를 50℃ 이하로 식힌 뒤, 상압 하에 3시간 환류시켜 상온으로 식혔다. 상온에서 메타아크릴레이트프로필트리메톡시실란 233.5중량부 및 글리시딜옥시프로필트리메톡시실란 5.3중량부를 혼합한 용액을 플라스크에 설치한 적하 깔때기를 이용하여 천천히 적하하였다. 이 무색 투명한 용액을 상압하에 가열하여 2시간 환류시켜 감광성의 유기 실록산 올리고머 a를 얻었다.The temperature of the solution synthesized as described above was cooled to 50 ° C. or lower, and refluxed under normal pressure for 3 hours to cool to room temperature. The solution which mixed 233.5 weight part of methacrylate propyl trimethoxysilane and 5.3 weight part of glycidyloxypropyl trimethoxysilane was dripped slowly at the normal temperature using the dropping funnel installed in the flask. This colorless transparent solution was heated to normal reflux for 2 hours to obtain a photosensitive organosiloxane oligomer a.
상기에서 얻은 감광성 유기 실록산 올리고머 a에 대하여 표 1의 비율로 첨가제를 혼합하고, 4℃에서 12시간 동안 숙성한 후, 0.2㎛의 PTFE (polytetrafluoroethylene) 필터로 여과하여, 조성물 A를 제조하였다.To the photosensitive organosiloxane oligomer a obtained above, the additives were mixed in a ratio of Table 1, aged at 4 ° C. for 12 hours, and then filtered through a 0.2 μm PTFE (polytetrafluoroethylene) filter to prepare a composition A.
표 1
조성 중량부
실록산 올리고머 a 57.0
PGMEA 28.5
TMPTA 8.4
DPHA 1.0
Irgacure 369 4.8
BYK333 0.3
Table 1
Furtherance Parts by weight
Siloxane oligomer a 57.0
PGMEA 28.5
TMPTA 8.4
DPHA 1.0
Irgacure 369 4.8
BYK333 0.3
PGMEA : 프로필렌글리콜모노메틸에테르아세테이트PGMEA: Propylene Glycol Monomethyl Ether Acetate
TMPTA : 트리메티롤프로판 트리아크릴레이트TMPTA: Trimethylolpropane triacrylate
DPHA : 디펜타에리스리콜 헥사아크릴레이트DPHA: dipentaerythroxy hexaacrylate
Irgacure 369 : 2-벤질-2-(디메틸아미노)-1-(4-몰포리노페닐)-1-부타논Irgacure 369: 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone
BYK 333 : BYK 사에 의해 시판되는 제품BYK 333: Products marketed by BYK
실시예 1Example 1
2㎛ 두께의 구리도선이 형성된 유리기판에 상기 조성물 A를 스핀코팅하고 120℃에서 1분간 건조하여 3㎛ 두께의 도막을 형성하였다. 조성물이 코팅된 유리기판을 자외선 노광기(MA6, SUSS Micro社)를 사용하여 하부 방향인 유리기판 면으로 100mJ/㎠의 광량으로 자외선을 조사하여 구리도선의 상부는 노출되지 않고 노출된 평탄화 부분만 경화가 되도록 하였다. 이어서, 경화된 코팅막을 30℃의 TMAH (tetramethyl ammonium hydroxide) 2.38% 용액에서 1분간 현상하여 노출되지 않은 미경화 부분을 제거하고, 경화된 상부 부분의 일부가 식각되어 평탄화되도록 하였고, 250℃에서 30분간 숙성하여 경도 5H, 투과율 98% 이상의 평탄화막을 형성하였다.The composition A was spin-coated on a glass substrate having a 2 μm thick copper wire and dried at 120 ° C. for 1 minute to form a 3 μm thick coating film. The glass substrate coated with the composition was irradiated with ultraviolet light at a light quantity of 100 mJ / cm 2 to the glass substrate surface in the downward direction using an ultraviolet exposure machine (MA6, SUSS Micro Co., Ltd.) to cure only the exposed flattened portion without exposing the upper portion of the copper conductor. Was made. The cured coating was then developed in a 2.38% solution of tetramethyl ammonium hydroxide (TMAH) at 30 ° C. for 1 minute to remove the unexposed portions, and a portion of the cured top portion was etched and flattened at 30 ° C. at 30 ° C. Aging was performed for a minute to form a planarization film having a hardness of 5H and a transmittance of 98% or more.
실시예 2Example 2
2㎛ 두께의 구리도선이 형성된 유리기판에 상기 조성물 A를 스핀코팅하고 120℃에서 1분간 건조하여 3㎛ 두께의 도막을 형성하였다. 조성물이 코팅된 유리기판을 자외선 노광기(MA6, SUSS Micro社)를 사용하여 하부 방향인 유리기판 면으로 200mJ/㎠의 광량으로 자외선을 조사하여 구리도선의 상부는 노출되지 않고 노출된 평탄화 부분만 경화가 되도록 하였다. 이어서, 경화된 코팅막을 30℃의 TMAH 2.38% 용액에서 1분간 현상하여 노출되지 않은 미경화 부분을 제거하고, 경화된 상부 부분의 일부가 식각되어 평탄화되도록 하였고, 250℃에서 30분간 숙성하여 경도 5H, 투과율 98% 이상의 평탄화막을 형성하였다.The composition A was spin-coated on a glass substrate having a 2 μm thick copper wire and dried at 120 ° C. for 1 minute to form a 3 μm thick coating film. The glass substrate coated with the composition was irradiated with ultraviolet light at a light quantity of 200 mJ / cm 2 to the glass substrate surface in the downward direction by using an ultraviolet exposure machine (MA6, SUSS Micro Co., Ltd.), thereby curing only the exposed flattened portion without exposing the upper portion of the copper conductor. Was made. Subsequently, the cured coating film was developed in a TMAH 2.38% solution at 30 ° C. for 1 minute to remove the unexposed part, and a part of the cured upper part was etched and planarized, and aged at 250 ° C. for 30 minutes to give a hardness of 5H. And a planarization film with a transmittance of 98% or more was formed.

Claims (11)

  1. 게이트가 형성된 기판 상에 자외선 경화형 유기실록산 수지층을 형성하는 단계;Forming an ultraviolet curable organosiloxane resin layer on the gate-formed substrate;
    상기 기판면의 하부방향으로 자외선을 조사하여, 경화 유기실록산 수지층을 형성하되, 게이트 상부에는 자외선에 노출되지 않게 하여 경화되지 않은 유기실록산 수지층이 남도록 하는 단계;Irradiating ultraviolet rays toward the lower side of the substrate to form a cured organosiloxane resin layer, wherein the cured organosiloxane resin layer is left on the gate so as not to be exposed to ultraviolet light;
    상기 경화되지 않은 유기실록산 수지층을 제거하는 단계; 및Removing the uncured organosiloxane resin layer; And
    상기 경화 유기실록산 수지층을 식각하는 단계를 포함하는 평탄화막의 형성방법.And forming the cured organosiloxane resin layer.
  2. 제 1항에 있어서,The method of claim 1,
    상기 자외선 경화형 유기실록산 수지층은 게이트 두께 이상으로 코팅하여 형성하는 것인 평탄화막의 형성방법.The UV curable organosiloxane resin layer is formed by coating a gate thickness or more.
  3. 제 1항에 있어서,The method of claim 1,
    상기 자외선의 광량은 50 내지 300mJ/㎠인 평탄화막의 형성방법.The amount of ultraviolet light is 50 to 300mJ / ㎠ method for forming a planarization film.
  4. 제1항에 있어서,The method of claim 1,
    상기 자외선 경화형 유기실록산 수지는 폴리스티렌 환산 중량 평균분자량이 100 내지 100,000인 감광성 유기 실록산 올리고머를 포함하는 것인 평탄화막의 형성방법.Wherein the ultraviolet curable organosiloxane resin comprises a photosensitive organosiloxane oligomer having a polystyrene equivalent weight average molecular weight of 100 to 100,000.
  5. 제 4항에 있어서,The method of claim 4, wherein
    상기 감광성 유기 실록산 올리고머는 실란을 가수분해 중합시켜 실록산 올리고머를 제조하고, 이어서 상기 실록산 올리고머에 감광성 기능을 부가하여 합성시킨 것인 평탄화막의 형성방법.The photosensitive organosiloxane oligomer is a hydrolysis-polymerized silane to produce a siloxane oligomer, and then a photosensitive function is added to the siloxane oligomer and synthesized.
  6. 제 5항에 있어서,The method of claim 5,
    상기 실란은 페닐트리메톡시실란, 페닐트리에톡시실란, 디페닐트리메톡시실란, 디페닐에톡시실란, 메틸트리에톡시실란, 메틸트리메톡시실란, 테트라메톡시실란, 테트라에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 디메틸디메톡시실란 및 디메틸디에톡시실란으로 이루어진 군에서 일종 이상 선택되는 것인 평탄화막의 형성방법.The silane may be phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane, diphenylethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, A method of forming a planarization film, which is at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane.
  7. 제 5항에 있어서,The method of claim 5,
    상기 감광성 기능을 부가하기 위한 화합물로 메타아크릴레이트프로필트리메톡시실란 또는 글리시딜옥시프로필트리메톡시실란이 선택되는 것인 평탄화막의 형성방법.Methaacrylate propyl trimethoxy silane or glycidyloxy propyl trimethoxy silane is selected as a compound for adding the photosensitive function.
  8. 제1항에 있어서,The method of claim 1,
    상기 자외선 경화형 유기실록산 수지는The ultraviolet curable organosiloxane resin is
    감광성 유기 실록산 올리고머 40 내지 70중량%;40 to 70% by weight of the photosensitive organosiloxane oligomer;
    유기 용매 10 내지 40중량%;10 to 40% by weight of the organic solvent;
    다관능기 (메타)아크릴 모노머 5 내지 20중량%;5 to 20% by weight of a multifunctional (meth) acrylic monomer;
    광개시제 3 내지 15 중량%; 및3 to 15 weight percent photoinitiator; And
    레벨링제 0.1 내지 2.0 중량%를 포함한 것으로부터 형성되는 평탄화막의 형성방법.A method of forming a flattening film formed from containing 0.1 to 2.0% by weight of a leveling agent.
  9. 제 1항에 있어서,The method of claim 1,
    상기 게이트는 1㎛ 이상의 두께를 갖는 것인 평탄화막의 형성방법.And the gate has a thickness of 1 μm or more.
  10. 제 1항에 있어서, The method of claim 1,
    상기 식각하는 단계 후에, 연필경도 5H 이상의 표면경도를 갖도록 150 내지 250℃에서 15분 내지 1시간 동안 숙성하는 단계를 더 포함하는 것인 평탄화막의 형성방법.After the etching step, further comprising the step of aging for 15 minutes to 1 hour at 150 to 250 ℃ to have a surface hardness of pencil hardness of 5H or more.
  11. 제 1항 내지 제 10항 중 어느 하나의 항에 따라 형성되는 평탄화막.A flattening film formed according to any one of claims 1 to 10.
PCT/KR2013/007689 2012-12-07 2013-08-27 Method for forming flattened film comprising uv curable organosiloxane resin, and flattened film formed thereby WO2014088189A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170185181A1 (en) * 2015-12-28 2017-06-29 Lg Display Co., Ltd. Display Device with Light Shield
CN110634794A (en) * 2019-09-27 2019-12-31 合肥鑫晟光电科技有限公司 Method for manufacturing display panel
US11084914B2 (en) 2017-12-20 2021-08-10 Rohm And Haas Electronic Materials Llc Hardcoat

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759638A (en) * 1994-09-06 1998-06-02 Toshiba Silicone Co., Ltd. Process for forming electronic circuit
KR20040090310A (en) * 2003-04-17 2004-10-22 주식회사 엘지화학 Organic Siloxane Resins and Insulating Film Using the Same
KR100826208B1 (en) * 2004-10-29 2008-04-30 주식회사 엘지화학 Method for preparing organic siloxane polymer and method for preparing insulating film using the same
KR20090045884A (en) * 2008-07-23 2009-05-08 한국기계연구원 Self-aligned organic thin film transistor and fabrication method thereof
KR20100029034A (en) * 2008-09-05 2010-03-15 제이에스알 가부시끼가이샤 Curable resin composition, set for forming resin cured film, protective film and process for forming protective film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759638A (en) * 1994-09-06 1998-06-02 Toshiba Silicone Co., Ltd. Process for forming electronic circuit
KR20040090310A (en) * 2003-04-17 2004-10-22 주식회사 엘지화학 Organic Siloxane Resins and Insulating Film Using the Same
KR100826208B1 (en) * 2004-10-29 2008-04-30 주식회사 엘지화학 Method for preparing organic siloxane polymer and method for preparing insulating film using the same
KR20090045884A (en) * 2008-07-23 2009-05-08 한국기계연구원 Self-aligned organic thin film transistor and fabrication method thereof
KR20100029034A (en) * 2008-09-05 2010-03-15 제이에스알 가부시끼가이샤 Curable resin composition, set for forming resin cured film, protective film and process for forming protective film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170185181A1 (en) * 2015-12-28 2017-06-29 Lg Display Co., Ltd. Display Device with Light Shield
US9965122B2 (en) * 2015-12-28 2018-05-08 Lg Display Co., Ltd. Display device with light shield
US11084914B2 (en) 2017-12-20 2021-08-10 Rohm And Haas Electronic Materials Llc Hardcoat
CN110634794A (en) * 2019-09-27 2019-12-31 合肥鑫晟光电科技有限公司 Method for manufacturing display panel
CN110634794B (en) * 2019-09-27 2023-04-07 合肥鑫晟光电科技有限公司 Method for manufacturing display panel

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