WO2011162461A1 - Électrode transparente et son procédé de production - Google Patents

Électrode transparente et son procédé de production Download PDF

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Publication number
WO2011162461A1
WO2011162461A1 PCT/KR2010/009584 KR2010009584W WO2011162461A1 WO 2011162461 A1 WO2011162461 A1 WO 2011162461A1 KR 2010009584 W KR2010009584 W KR 2010009584W WO 2011162461 A1 WO2011162461 A1 WO 2011162461A1
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WIPO (PCT)
Prior art keywords
metal film
transparent electrode
substrate
present
light transmittance
Prior art date
Application number
PCT/KR2010/009584
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English (en)
Korean (ko)
Inventor
최경철
이성민
박오옥
최홍균
Original Assignee
한국과학기술원
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Application filed by 한국과학기술원 filed Critical 한국과학기술원
Priority to KR1020137002098A priority Critical patent/KR101477291B1/ko
Publication of WO2011162461A1 publication Critical patent/WO2011162461A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials
    • 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
    • G02F2203/00—Function characteristic
    • G02F2203/10—Function characteristic plasmon

Definitions

  • the present invention relates to a transparent electrode and a method of manufacturing the same. More particularly, the present invention relates to a transparent electrode usable as an electrode, such as a display element or a flexible display, and a manufacturing method thereof.
  • an oxide-based compound such as Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) having high light transmittance in the visible light band is used.
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • the transparent electrode made of the oxide-based compound as described above has a high resistance because of its low electrical conductivity, so when applied to a flat panel display or a thin film solar cell, the performance of the device is deteriorated and the size is disadvantageous. there was.
  • indium which is a major component of the oxide-based compound, has a scarcity, the burden of price increase is always present, and thus a new material that can replace the oxide-based compound is in the spotlight.
  • the light transmittance in the visible light band is very low, and thus it is difficult to use it as a material of a transparent electrode.
  • the metal film is an oxide such as ITO.
  • transparent electrodes have been developed by arranging between transparent films of inorganic series or inorganic films, such transparent electrodes have secured light transmittance in the visible light band, but are limited in securing sufficient electrical conductivity because the thickness of metal film is 10 nm or less. There was a problem that occurred.
  • the present invention has been made to solve the above problems, and instead of reducing the thickness of the metal film, it is sufficient to minimize the high light transmittance and electrical resistance in the visible light band by forming a plurality of fine holes arranged at predetermined intervals in the metal film. It is an object to provide a transparent electrode capable of maintaining electrical conductivity and a method of manufacturing the same.
  • a transparent electrode includes a substrate having a predetermined dielectric constant; And a metal film formed on the substrate, wherein the metal film includes a plurality of fine holes arranged at predetermined intervals to improve light transmittance due to surface plasmon resonance.
  • the method of manufacturing a transparent electrode comprises the steps of fusion bonding the plasma-etched particles to the metal film formed on the substrate; And removing the particles fused to the metal film to form a metal film having a plurality of micro holes arranged at predetermined intervals on the substrate.
  • the cost of manufacturing a transparent electrode is reduced because it is made of a metal which is less expensive than an oxide-based compound and has a low light resistance due to excellent light transmittance and high electrical conductivity in the visible light band which can be used as a transparent electrode. It has an effect that can be made.
  • the metal is made of a material and has a high ductility, it has an effect that can be utilized in a device such as a flexible display in which a conventional oxide-based transparent electrode is hardly applied.
  • FIG. 1 is a perspective view of a transparent electrode according to a preferred embodiment of the present invention
  • Figure 3 is a reference graph for the light transmittance according to the fine hole diameter of the transparent electrode according to an embodiment of the present invention
  • FIG. 4 is a reference graph for light transmittance according to a metal film thickness of a transparent electrode according to a preferred embodiment of the present invention.
  • FIG. 5 is a reference graph for light transmittance according to mutual spacing of each of the plurality of micro holes arranged on the metal film of the transparent electrode according to the preferred embodiment of the present invention
  • FIG. 6 is a perspective view of a transparent electrode according to another preferred embodiment of the present invention.
  • FIG. 7 is a reference graph of light transmittance in a visible light band of a transparent electrode according to another preferred embodiment of the present invention.
  • FIG. 8 is a flowchart illustrating a method of manufacturing a transparent electrode according to a preferred embodiment of the present invention.
  • FIG. 9 is a reference diagram for a method of manufacturing a transparent electrode according to a preferred embodiment of the present invention.
  • FIG. 1 is a perspective view of a transparent electrode according to a preferred embodiment of the present invention.
  • a transparent electrode 1a As shown in FIG. 1, a transparent electrode 1a according to a preferred embodiment of the present invention includes a substrate 10a and a metal film 20a.
  • the substrate 10a may be a flexible transparent plastic material such as polyether terephthlate (PET) and polyethersulfone (PES) having a predetermined dielectric constant.
  • PET polyether terephthlate
  • PES polyethersulfone
  • the material of the substrate 10a is not limited thereto, and when the substrate 10a is used as a transparent electrode that does not require flexible characteristics, the substrate 10a may be made of glass.
  • the metal film 20a may be formed on the substrate 10a, and a plurality of micro holes 25a may be formed, two-dimensionally arranged at predetermined intervals, for a light transmissive shape due to surface plasmon resonance.
  • the metal film 20a may be a silver metal film having a thickness of 20 nm to 50 nm, and the shape of the fine hole 25a may be a circular shape having a predetermined diameter.
  • the material of the metal film 20a is not limited thereto, and other metal materials, indium tin oxide (ITO), or indium zinc oxide (IZO) may be used as the material of the metal film 20a.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • each of the plurality of micro holes 25a arranged in the metal film 20a may be 45 nm to 250 nm, and each of the plurality of micro holes 25a may have a diameter of 25 nm to 100 nm.
  • the reason for arranging the plurality of fine holes 25a at predetermined intervals in the metal film 20a of the transparent electrode 1a according to the preferred embodiment of the present invention will be described below with reference to FIG. 2.
  • the thickness of the metal film 20a of the transparent electrode 1a, the mutual spacing of each of the plurality of fine holes 25a, and the diameter of each of the plurality of fine holes 25a are presented within the above ranges. 5 to be described.
  • FIG. 2 is a reference diagram for a surface plasmon resonance phenomenon occurring around the micro holes arranged in the metal film.
  • surface plasmon resonance refers to a phenomenon in which the metal nanoparticles resonate with light having a specific wavelength in the visible or near infrared band so that the surface plasmons of the metal nanoparticles vibrate collectively.
  • FDTD finite difference time domain
  • 3 is a reference graph of the light transmittance according to the fine hole diameter of the transparent electrode of the present invention.
  • the thickness of the metal film 20a and the mutual spacing of each of the plurality of micro holes 25a arranged in the metal film 20a are fixed to 25 nm and 45 nm, respectively.
  • the plurality of fine holes 25a are not arranged in a state where the thickness of the metal film 20a and the mutual spacing of the plurality of fine holes 25a arranged in the metal film 20a are fixed to each other. Comparing the light transmittance of the film 20a and the metal film 20a in which the plurality of fine holes 25a having diameters of 20 nm, 30 nm, and 36 nm are arranged, the metal film having the plurality of fine holes 25a arranged therein ( 20a may have a high light transmittance in the visible light band when compared to the metal film 20a in which the micro holes 25a are not arranged, and the size of the micro holes 25a and the light transmittance in the visible light band. It can be seen that is proportional to.
  • the overall aperture ratio increases as the diameter of each of the plurality of micro holes 25a arranged in the metal film 20a increases, so that the light transmittance in the visible light region also increases, but conversely is arranged in the metal film 20a.
  • Increasing the diameter of each of the plurality of micro holes 25a excessively decreases the intensity of plasmon resonance, thereby reducing light transmittance.
  • each of the plurality of fine holes 25a arranged in the metal film 20a is increased, the area of the metal film 20a is reduced, and thus the electrical conductivity is lowered, thereby increasing the resistance.
  • the diameter of each of the plurality of fine holes 25a arranged in 20a is preferably 25 nm to 100 nm, which is the range given above.
  • FIG. 4 is a reference graph of light transmittance according to a metal film thickness of a transparent electrode according to a preferred embodiment of the present invention.
  • the diameter of each of the plurality of micro holes 25a arranged in the metal film 20a and the mutual spacing of each of the plurality of micro holes 25a arranged in the metal film 20a are fixed to 30 nm and 60 nm, respectively. It was.
  • the diameters of the plurality of fine holes 25a arranged in the metal film 20a and the mutual spacing of each of the plurality of fine holes 25 formed in the metal film 20 are kept constant.
  • the thickness of the metal film 20a is changed to 20 nm, 50 nm, and 100 nm, respectively, and the light transmittances in the visible light bands are compared, the thickness of the metal film 20a increases, and thus the plurality of metal films 20a are arranged in the metal film 20a. Since the intensity of plasmon resonance generated around each of the fine holes 25a increases, light transmittance in the visible light band may increase.
  • the thickness of the metal film 20a when the thickness of the metal film 20a is increased, the light transmittance in the visible light band is increased, but accordingly, the light transmittance of the metal film 20a itself is reduced, so that the thickness of the metal film 20a is in the range of 20 nm to the previously presented range. 50 nm is preferred.
  • FIG 5 is a light transmittance graph according to the mutual spacing of each of the plurality of micro holes arranged in the metal film of the transparent electrode according to the preferred embodiment of the present invention.
  • the thickness of the metal film 20a in FIG. 5 was fixed to 100 nm.
  • the mutual spacing of the plurality of micro holes 25a arranged in the metal film 20a with the thickness of the metal film 20a fixed at 100 nm is 45 nm, 60 nm, 100 nm, and 350 nm, respectively.
  • the light transmittance in the visible light band increases as the mutual spacing of each of the plurality of micro holes 25a arranged in the metal film 20a increases.
  • the light transmittance in the visible light band is increased, but the area where the light transmittance is increased due to the plasmon resonance phenomenon is red. Since the red-shift is excessively increased when the mutual spacing of each of the plurality of micro holes 25a arranged in the metal film 20a is excessively increased, the area where the light transmittance is increased is over the infrared band instead of the visible light band. It can be confirmed that it is not suitable for the electrode.
  • the mutual spacing of each of the plurality of micro holes 25a arranged in the metal film 20a is in the range given above, and the range in which the light transmittance increases due to the plasmon resonance phenomenon lies in the visible light band. desirable.
  • FIG. 6 is a perspective view of a transparent electrode according to another preferred embodiment of the present invention.
  • the flexible transparent electrode 1b is formed on the substrate 10b and has a predetermined spacing for improving light transmittance due to surface plasmon resonance.
  • the transparent inorganic film 30b is formed on the metal film 20b including the plurality of fine holes 25b arranged in (eg, two-dimensional array).
  • the transparent inorganic layer 30b may be formed of a silicon dioxide (SiO 2) material or the same material as the substrate 10b.
  • FIG. 7 is a reference graph of light transmittance in a visible light band of a transparent electrode according to another exemplary embodiment of the present invention.
  • the thickness of the metal film 20b is fixed to 50 nm in FIG. 7, and the transparent inorganic film 30b of silicon dioxide is formed on the metal film 20b as illustrated in FIG. 7 (bold line in FIG. 7). Part) It can be seen that the light transmittance in the visible light region is better than that in the case where the transparent inorganic film 30b is not formed (solid line part in FIG. 7).
  • the size of the plasmon resonance is further increased by the cross-coupled surface plasmon. It becomes possible to manufacture an electrode.
  • FIG. 8 is a flowchart illustrating a method of manufacturing a transparent electrode according to an exemplary embodiment of the present invention
  • FIG. 9 is a reference diagram of a method of manufacturing a transparent electrode according to an exemplary embodiment of the present invention.
  • a method of manufacturing a flexible transparent electrode having a metal film according to a preferred embodiment of the present invention is as follows.
  • Plasma-etched colloidal self-assembling nanoparticles P1 arranged on a predetermined substrate (eg, a glass or metal substrate) in S10 (FIGS. 9A and 9B).
  • S10 self-assembled nanoparticles (for example, nanoparticles of gold material or nanoparticles of other metal material having a higher melting point than silver) may be arranged in the form of a plurality of layers of two or more layers,
  • the plasma etching is performed to form a plurality of fine holes 25a arranged in the metal film 20a at predetermined intervals and each having a predetermined size, and thus an oxygen plasma etching method may be used.
  • the self-assembled nanoparticles P2 etched in S20 are fused to the upper portion of the metal film 20a. ((C) and (d) of FIG. 9).
  • S20 is a method of attaching the etched self-assembled nanoparticles (P2) to the lower surface of the viscous PDMS (PolyDiMethylSiloxane) after transition to PDMS (Fig. 9 (c)) is formed in advance on the substrate 10a
  • the etched self-assembled nanoparticles P2 are brought into contact with the seed metal layer sl, which is etched, and heated by a heater disposed on the bottom surface of the substrate 10a to etch the self-assembled self-assembled particles attached to the bottom surface of the PDMS.
  • the nanoparticles P2 are separated from the bottom surface of the PDMS, the nanoparticles P2 are fused onto the seed metal layer sl (FIG. 9D), and the metal plating layer is formed on the seed metal layer sl by electroplating. (el) forming a step (e) of FIG.
  • the seed metal layer sl and the metal plating layer el may be silver metal layers.
  • the method may further include etching the seed metal layer sl of the metal film 20a so that the fine holes 25a formed in the metal film 20a pass through the metal film 20a after S30. 9 (g))
  • the transparent electrodes 1a and 1b of the present invention are a metal film 20a in which a plurality of fine holes 25a and 25b having a predetermined interval are arranged on a glass or a flexible transparent plastic substrate 10a and 10b having a predetermined dielectric constant.
  • 20b or a transparent inorganic film 30b of the same material as the silicon dioxide material or the substrate 10b is formed on the metal film 20b on which the plurality of fine holes 25b having a predetermined interval are arranged.
  • the surface plasmon resonance phenomenon occurring around each of the plurality of micro holes 25a and 25b improves light transmittance in the visible light band and minimizes resistance due to the high electrical conductivity of the metal itself. Since the manufacturing cost is lower than the transparent electrode of the compound material of the series, the manufacturing cost of the transparent electrode (for example, a transparent electrode used in a flat panel display or a thin film solar cell) can be greatly reduced.
  • the ductility is excellent in comparison with the transparent electrode of the conventional oxide-based compound material, when the transparent electrode of the present invention is configured on a flexible transparent plastic substrate, the flexible electrode of the conventional oxide-based compound material could not be applied. It has the effect which can be utilized for a display.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
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  • Electroluminescent Light Sources (AREA)
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Abstract

La présente invention concerne une électrode transparente souple comprenant un film métallique ainsi que son procédé de production. De manière plus spécifique, l'invention concerne une électrode transparente souple comprenant un film métallique qui peut être utilisée comme une électrode pour un élément d'affichage ou un affichage souple ou analogue, ainsi que son procédé de production. La présente invention comporte: un substrat ayant une constante diélectrique prédéterminée ; et un film métallique formé sur la partie supérieure du substrat, le film métallique comprenant une pluralité de micro-trous disposés à intervalles prédéterminés afin d'améliorer la transparence optique au moyen de résonance de plasmons de surface. Comparée aux composés à base d'oxyde, la présente invention procure des effets avantageux en ce que les coûts de production d'électrodes transparentes peuvent être réduits étant donné l'utilisation d'un métal peu coûteux comme matière première et qu'il y a une excellente transparence optique dans la bande de lumière visible à laquelle l'invention peut être utilisée sous forme d'une électrode transparente et qu'il y a une caractéristique de faible résistance due à une conductivité électrique élevée.
PCT/KR2010/009584 2010-06-25 2010-12-30 Électrode transparente et son procédé de production WO2011162461A1 (fr)

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KR20100060668 2010-06-25

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CN109471283A (zh) * 2017-09-07 2019-03-15 乐金显示有限公司 包括液晶胶囊的液晶显示装置及其制造方法
CN113496790A (zh) * 2021-07-06 2021-10-12 浙江大学 一种柔性透明电极

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KR102664438B1 (ko) 2016-09-23 2024-05-14 삼성디스플레이 주식회사 표시 장치
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Publication number Priority date Publication date Assignee Title
CN109471283A (zh) * 2017-09-07 2019-03-15 乐金显示有限公司 包括液晶胶囊的液晶显示装置及其制造方法
CN113496790A (zh) * 2021-07-06 2021-10-12 浙江大学 一种柔性透明电极
CN113496790B (zh) * 2021-07-06 2022-04-22 浙江大学 一种柔性透明电极

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