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WO2009131257A1 - Conductive polymer transparent electrode and fabricating method thereof - Google Patents

Conductive polymer transparent electrode and fabricating method thereof Download PDF

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Publication number
WO2009131257A1
WO2009131257A1 PCT/KR2008/002236 KR2008002236W WO2009131257A1 WO 2009131257 A1 WO2009131257 A1 WO 2009131257A1 KR 2008002236 W KR2008002236 W KR 2008002236W WO 2009131257 A1 WO2009131257 A1 WO 2009131257A1
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WO
WIPO (PCT)
Prior art keywords
conductive polymer
substrate
transparent electrode
fabricating
capillary
Prior art date
Application number
PCT/KR2008/002236
Other languages
French (fr)
Inventor
Dong-Soo Kim
Kang-Dae Kim
Jeong-Dai Jo
Original Assignee
Korea Institute Of Machinery & Materials
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Institute Of Machinery & Materials filed Critical Korea Institute Of Machinery & Materials
Priority to PCT/KR2008/002236 priority Critical patent/WO2009131257A1/en
Publication of WO2009131257A1 publication Critical patent/WO2009131257A1/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/0126—Dispenser, e.g. for solder paste, for supplying conductive paste for screen printing or for filling holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/105—Using an electrical field; Special methods of applying an electric potential

Definitions

  • the present invention relates to a transparent electrode and specifically a technique that conductive polymer particles are laminated on a substrate by an electrostatic spray printing method.
  • Transparent electrodes have high conductivity and high transmission in the visible light range, and thus are widely used as various display devices such as LCD and OLED, various photo detectors such as image sensors, electrodes such as solar cells, and the like.
  • Tin-doped indium oxide that is, indium tin oxide (ITO) is primarily used as materials of transparent electrodes, and antimony- or fluorine-doped tin oxide, aluminum- or gallium-doped zinc oxide, and the like are also used.
  • the object of the present invention is to provide a conductive polymer transparent electrode, wherein the transparent electrode is prepared using conductive polymer materials instead of the existing metal oxides, which may be easi Iy formed on even a plastic substrate and has an excel lent electrical property, and a method of fabricating the same.
  • the present invention provides a method of fabricating a transparent electrode comprising laminating conductive polymer particles on a substrate by an electrostatic spray printing method.
  • the method of fabricating the conductive polymer transparent electrode according to the present invention comprises steps of placing a substrate on a substrate holder, filling a conductive polymer ink into a capillary, which is placed upward said substrate, applying voltage in said conductive polymer ink within said capillary, in a state that said substrate holder is grounded, and inducing said conductive ink toward said substrate, so that said conductive polymer particles are laminated on a surface of said substrate to form the transparent electrode, wherein said conductive polymer ink is sprayed from said capillary, with concentrating electric field at the end of said capillary.
  • the method of fabricating the conductive polymer transparent electrode according to the present invention may further comprise a step of forming a mask pattern on the surface of said substrate, wherein said conductive polymer particles in sad step of forming the transparent electrode are laminated on the surface of said substrate exposed to outside in said mask pattern.
  • said conductive polymer particle is preferably polyethylenedioxythiophene polystyrenesulfonate, and may be one selected from polyethylenedioxythiophene, polyacetylene, polypyrrole, polythiophene and polyaniline.
  • an additive is polyalcohol.
  • Said substrate may be a plastic substrate, and said step of forming the transparent substrate may be carried out in a state that said substrate holder is rotated.
  • the method of fabricating the conductive polymer transparent electrode according to the present invention may further comprise a step of installing a guide ring near to the lower end of said capillary for said conductive polymer ink to be controlled toward said substrate and forming a collimating electrode on the top of said substrate. It may further comprise a step of thermally hardening said transparent electrode at about 180 ° C or less.
  • the present invention provides a conductive polymer transparent electrode fabricated by such a method.
  • the present invention provides a method of fabricating a transparent electrode by using conductive polymer materials instead of the existing metal oxides, it may solve the problem of the metal oxide transparent electrodes, and the electrostatic spray printing method, wherein the conductive polymer particles are laminated on the substrate, has an advantage that the transparent electrode may be easily fabricated on even a plastic substrate.
  • the conductive polymer transparent electrode fabricated by the fabricating method according to the present invention does not only have very excellent film uniformity and denseness, but also exhibit excellent property enough to compete with the existing metal oxide transparent electrodes, even in terms of electric conductivity, since the conductive polymer materials are laminated on the substrate, with having electrostatic force.
  • Fig. l is a concept view of the electrostatic spray printing method used in fabricating a conductive polymer transparent electrode according to the present invention.
  • Fig. 2 is a schematic view showing a method ol fabricating a conductive polymer transparent electrode according to examples of the present invention.
  • Figs. 3 and 4 are plane and section photographs of the conductive polymer transparent electrode according to experimental examples of the present invention. [Best Mode]
  • Fig. l is a concept view of the electrostatic spray printing method used in fabricating a conductive polymer transparent electrode according to the present invention.
  • the electrostatic spray print ing method is a technique that charged conductive polymer particles (10a) are induced by electric field between a substrate (11) and a capillary (12) and formed on the substrate (11).
  • a conductive polymer ink (10) is fil led into the capillary (12), wherein an additive is added to the conductive polymer ink (10) to improve spraying state and electric conductivity.
  • the substrate (11) which is a subject to form the conductive polymer transparent electrode thereon, is placed distant from the capillary (12) as a predetermined distance. If a high voltage is applied to the conductive polymer ink (10) in the capillary (12) in a state that the substrate (11) is grounded (practically, a substrate holder for supporting the substrate is grounded), an extremely large electric field is produced at the end of the capillary (12) by an effect of concentrating electric field.
  • intensity, E c of the electric field can be calculated by the following mathematical formula'- [Mathematical Formula 1]
  • V c is the applied voltage
  • r c is an outer diameter of the capillary end
  • d is a distance from the capillary to the substrate.
  • the electric field concentrated at the end part of the capillary (12) separates conductive polymer materials into positive and negative ions to produce ionized particles, i.e., charged particles (10a).
  • the charged particles (10a) are concentrated on the solution surface and are jetted from the capillary (12), as the surface is unstable.
  • the jetted fine droplets are induced toward the substrate (11) by the electric field and laminated on the substrate (11) in the form of micronized particles.
  • Fig. 2 is a schematic view showing a method of fabricating a conductive polymer transparent electrode according to examples of the present invention.
  • the substrate (11) is placed on a rotatable substrate holder (14) and the same mask pattern (13) as a stencil mask is formed on the surface of the substrate (11).
  • the mask pattern (13) determines a pattern of the transparent electrode to be formed on the substrate (11).
  • the mask pattern (13) may be also fixed via a mask holder (not depicted).
  • the substrate (11) glass substrates or plastic substrates of various materials may be used.
  • the substrates are not surely limited to these substrates, but substrates having various materials or types may be used.
  • plastic substrates as their materials, polyethylene naphthalate (PEN) , polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), polyimide (PI), and the like may be used.
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PES polyethersulfone
  • PI polyimide
  • the capillary (12), in which the conductive polymer ink (10) is filled, is placed upward the mask pattern (13).
  • the capillary (12) is distant from the substrate (11) as a predetermined distance, wherein the bottom end part (12a) toward the substrate has a pointed shape.
  • any additive is added to the conductive polymer ink (10) to improve the spraying state and the electric conductivity.
  • polyethylenedioxythiophene PEDOT
  • polyacetylene polypyrrole
  • polythiophene polyaniline and the like
  • polyethylenedioxythiophene polystyrenesul fonate PEDOT:PSS
  • the present invention is not surely limited to these materials, but any polymer material having transparency and electric conductivity may be applied.
  • polyalcohol such as glycerol or sorbitol is used.
  • An electrode (15) is inserted at the top of the capillary (12) and placed inside the conductive polymer ink (10).
  • the electrode (15) is connected to a first power source (16a) which may apply high voltage.
  • a gas injecting tube (17) may be further connected to the top of the capillary (12) to increase spray efficiency, on jetting the conductive polymer ink (10).
  • a guide ring (18a) may be further instal led near to the bottom end part (12a) of the capillary (12), and a collimating electrode (18b) and a Teflon sheet (18c) may be further installed at the upper of the mask pattern (13).
  • the guide ring (18a) and the collimating electrode (18b) are connected to a second power source (16b), which serve for the conductive polymer ink (10) jetted from the capillary (12) to be controlled toward the substrate (11).
  • the Teflon sheet (18c) is a shielding screen prevent ing the jetted conductive polymer ink (10) or particles (10a) from escaping outside.
  • the electrostatic spray printing process is carried out by the principle described above. That is, the conductive polymer ink (10) is sprayed from the capillary (12), with concentrating electric field at the bottom end part (12a) of the capillary (12), and the sprayed conductive polymer ink (10) is induced toward the substrate (11) by the electrostatic force.
  • the conductive polymer ink (10) is laminated on the substrate (11) in a form of very small particles. Therefore, the conductive polymer particles (10a) are laminated on the specific surface area of the substrate (11) exposed to the outside of the mask pattern (13) to form the transparent electrode.
  • the transparent electrode is sufficiently dried, to prevent a defect such as a pinhole from being developed and improve its optical properties.
  • This step may be, for example, carrying out a process of thermally hardening at about 180 ° C or less for several tens minutes.
  • voltage may be separately applied to the guide ring (18a) and the collimating electrode (18b) via the second power source (16b) and the substrate (11) maybe rotated via the substrate holder (14). These contribute to improve uniformity and denseness of the transparent electrode. However, these may be optionally selected.
  • the electrostatic spray printing method according to the present invention may greatly improve film uniformity and denseness of the transparent electrode over the existing spin coating.
  • a general OHP film was used as the substrate, and PEDOT ⁇ PSS and glycerol were mixed in a ratio of 10:6, respectively, and used as the conductive polymer material and the additive.
  • the conductive polymer material Baytron PH 500 product from H. C. Starck company was used.
  • the high voltage applied via the first power source was 7 kV, and no voltage was applied via the second power source.
  • the time of vapor depositing is two hours, and then a drying process was carried out at 120 ° C for 30 minutes.
  • the transparent electrode was fabricated by using the existing spin coating from the same substrate and conductive polymer material as above. It was as a process condition of the spin coating to rotate at 500 rpm for 10 seconds and then at 1000 rpm for 15 seconds. The condition of drying was the same.
  • An electrical property assay was to measure each sheet resistance of the transparent electrodes using the known 4-point probe system.
  • the values of sheet resistance were not uniform as 90 ⁇ /O to several k ⁇ /rj.
  • the values of sheet resistance were uniform as 24 ⁇ /D, 27 ⁇ /G, 40 ⁇ /D, and 27 ⁇ /D, and the average value was only 30 ⁇ /D.
  • Figs. 3 and 4 are plane and section photographs of the conductive polymer transparent electrode according to experimental examples of the present invention.
  • root-mean-square (RMS) roughness of the transparent electrode was only about 4.6 nm.
  • thickness of the transparent electrode was about 650 nm. Therefore, it could be known that the conductive polymer transparent electrode of the present invention had very excellent uniformity.
  • the present invention provides a method of fabricating a transparent electrode by using conductive polymer materials instead of the existing metal oxides, it may solve the problem of the metal oxide transparent electrodes, and the electrostatic spray printing method, wherein the conductive polymer particles are laminated on the substrate, has an advantage that the transparent electrode may be easily fabricated on even a plastic substrate.
  • the conductive polymer transparent electrode fabricated by the fabricating method according to the present invention does not only have very excellent film uniformity and denseness, but also exhibit excellent property enough to compete with the existing metal oxide transparent electrodes, even in terms of electric conductivity, since the conductive polymer materials are laminated on the substrate, with having electrostatic force.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention relates to a conductive polymer transparent electrode and a method of fabricating the same, and fabricates the transparent electrode by laminating conductive polymer particles on a substrate using an electrostatic spray printing method. According to the present invention, the substrate is placed on a substrate holder, a mask pattern is formed on a surface of the substrate, and then a conductive polymer ink is filled in a capillary, which is placed upward the mask pattern, and voltage is applied to the conductive polymer ink in the capillary, in a state that the substrate holder is grounded. Thus, said conductive ink is induced toward said substrate, so that said conductive polymer particles are laminated on a surface of said substrate to form the transparent electrode, wherein said conductive polymer ink is sprayed from said capillary, with concentrating electric field at the end of said capillary. The present invention may easily fabricate the transparent electrode on even a plastic substrate, and provides the conductive polymer transparent electrode having excellent property enough to compete with the existing metal oxide transparent electrodes.

Description

[DESCRIPTION] [Invention Title]
Conductive Polymer Transparent Electrode and Fabricating Method Thereof [Technical Field]
The present invention relates to a transparent electrode and specifically a technique that conductive polymer particles are laminated on a substrate by an electrostatic spray printing method. [Background Art]
Transparent electrodes have high conductivity and high transmission in the visible light range, and thus are widely used as various display devices such as LCD and OLED, various photo detectors such as image sensors, electrodes such as solar cells, and the like. Tin-doped indium oxide, that is, indium tin oxide (ITO) is primarily used as materials of transparent electrodes, and antimony- or fluorine-doped tin oxide, aluminum- or gallium-doped zinc oxide, and the like are also used.
However, conventional transparent electrodes based on such metal oxides require basically a vacuum process for preparing electrode thin films. Therefore, they do not only cost high, but are also unsuitable to a flexible product needing flexibility due to their brittleness or fragileness.
Recently, as an alternative for solving these problems, techniques, which prepare transparent electrodes by using transparent conductive polymer materials, have been actively studied. Techniques of patterning conductive polymer materials have been proposed in US Patent Nos.5,447,824 and 5,976,284, wherein examples of polymer materials, such as polyethylenedioxythiophene (PEDOT), polyacetylene, polypyrrole, polythiophene, and polyaniline, are introduced.
However, the technical field pertaining to the present invention leans toward a side of developing materials yet, and has poor studies for developing processes. There is a disadvantage that conventional conductive polymer transparent electrodes have insufficient electric conductivity. If conventional conductive polymer transparent electrodes compete with the existing metal oxide transparent electrodes, they must have a sheet resistance of several tens Ω/D. But, the sheet resistance in conventional conductive polymer transparent electrodes reach several hundreds Ω/D to several kΩ/D.
[Disclosure]
[Technical Problem]
Accordingly, the object of the present invention is to provide a conductive polymer transparent electrode, wherein the transparent electrode is prepared using conductive polymer materials instead of the existing metal oxides, which may be easi Iy formed on even a plastic substrate and has an excel lent electrical property, and a method of fabricating the same.
[Technical Solution]
To achieve this object, the present invention provides a method of fabricating a transparent electrode comprising laminating conductive polymer particles on a substrate by an electrostatic spray printing method.
The method of fabricating the conductive polymer transparent electrode according to the present invention comprises steps of placing a substrate on a substrate holder, filling a conductive polymer ink into a capillary, which is placed upward said substrate, applying voltage in said conductive polymer ink within said capillary, in a state that said substrate holder is grounded, and inducing said conductive ink toward said substrate, so that said conductive polymer particles are laminated on a surface of said substrate to form the transparent electrode, wherein said conductive polymer ink is sprayed from said capillary, with concentrating electric field at the end of said capillary.
The method of fabricating the conductive polymer transparent electrode according to the present invention may further comprise a step of forming a mask pattern on the surface of said substrate, wherein said conductive polymer particles in sad step of forming the transparent electrode are laminated on the surface of said substrate exposed to outside in said mask pattern.
In the method of fabricating the conductive polymer transparent electrode according to the present invention, said conductive polymer particle is preferably polyethylenedioxythiophene polystyrenesulfonate, and may be one selected from polyethylenedioxythiophene, polyacetylene, polypyrrole, polythiophene and polyaniline. Preferably, an additive is polyalcohol.
Said substrate may be a plastic substrate, and said step of forming the transparent substrate may be carried out in a state that said substrate holder is rotated.
The method of fabricating the conductive polymer transparent electrode according to the present invention may further comprise a step of installing a guide ring near to the lower end of said capillary for said conductive polymer ink to be controlled toward said substrate and forming a collimating electrode on the top of said substrate. It may further comprise a step of thermally hardening said transparent electrode at about 180 °C or less.
In addition, the present invention provides a conductive polymer transparent electrode fabricated by such a method. [Advantageous Effects]
Since the present invention provides a method of fabricating a transparent electrode by using conductive polymer materials instead of the existing metal oxides, it may solve the problem of the metal oxide transparent electrodes, and the electrostatic spray printing method, wherein the conductive polymer particles are laminated on the substrate, has an advantage that the transparent electrode may be easily fabricated on even a plastic substrate.
In addition, the conductive polymer transparent electrode fabricated by the fabricating method according to the present invention does not only have very excellent film uniformity and denseness, but also exhibit excellent property enough to compete with the existing metal oxide transparent electrodes, even in terms of electric conductivity, since the conductive polymer materials are laminated on the substrate, with having electrostatic force. [Description of Drawings]
Fig. l is a concept view of the electrostatic spray printing method used in fabricating a conductive polymer transparent electrode according to the present invention.
Fig. 2 is a schematic view showing a method ol fabricating a conductive polymer transparent electrode according to examples of the present invention.
Figs. 3 and 4 are plane and section photographs of the conductive polymer transparent electrode according to experimental examples of the present invention. [Best Mode]
Examples of the present invention are explained in more detail below, with reference with the attached drawings. However, in explaining the examples, technical contexts that are well known in the art to which the present invention pertains and are not directly connected with the present invention are omitted as much as possible. This is intended for the present invention to be clearly informed without dimming its kernel, by omitting unnecessary descriptions.
In addition, some components in the attached drawings are exaggerated, omitted, or schematically depicted, and the size of each component does not entirely reflect its actual size. Over the attached drawings, the same or corresponding components indicate the same reference numerals.
Fig. l is a concept view of the electrostatic spray printing method used in fabricating a conductive polymer transparent electrode according to the present invention.
Referring to Fig.1, the electrostatic spray print ing method is a technique that charged conductive polymer particles (10a) are induced by electric field between a substrate (11) and a capillary (12) and formed on the substrate (11).
Specif ically explaining, a conductive polymer ink (10) is fil led into the capillary (12), wherein an additive is added to the conductive polymer ink (10) to improve spraying state and electric conductivity. The substrate (11), which is a subject to form the conductive polymer transparent electrode thereon, is placed distant from the capillary (12) as a predetermined distance. If a high voltage is applied to the conductive polymer ink (10) in the capillary (12) in a state that the substrate (11) is grounded (practically, a substrate holder for supporting the substrate is grounded), an extremely large electric field is produced at the end of the capillary (12) by an effect of concentrating electric field. Here, intensity, Ec, of the electric field can be calculated by the following mathematical formula'- [Mathematical Formula 1]
2Vc r In(AdIrr) wherein, Vc is the applied voltage, rc is an outer diameter of the capillary end, and d is a distance from the capillary to the substrate. As can be seen from the above formula, if the applied voltage is increased and the outer diameter of the capillary end is decreased, then the intensity of concentrating electric field is increased.
The electric field concentrated at the end part of the capillary (12) separates conductive polymer materials into positive and negative ions to produce ionized particles, i.e., charged particles (10a). The charged particles (10a) are concentrated on the solution surface and are jetted from the capillary (12), as the surface is unstable. The jetted fine droplets are induced toward the substrate (11) by the electric field and laminated on the substrate (11) in the form of micronized particles.
The method of fabricating the conductive polymer transparent electrode using such an electrostatic spray printing method is specifically explained via examples below. Fig. 2 is a schematic view showing a method of fabricating a conductive polymer transparent electrode according to examples of the present invention.
Referring to Fig.2, the substrate (11) is placed on a rotatable substrate holder (14) and the same mask pattern (13) as a stencil mask is formed on the surface of the substrate (11). The mask pattern (13) determines a pattern of the transparent electrode to be formed on the substrate (11). The mask pattern (13) may be also fixed via a mask holder (not depicted).
As the substrate (11), glass substrates or plastic substrates of various materials may be used. However, the substrates are not surely limited to these substrates, but substrates having various materials or types may be used. In case of plastic substrates, as their materials, polyethylene naphthalate (PEN) , polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), polyimide (PI), and the like may be used.
The capillary (12), in which the conductive polymer ink (10) is filled, is placed upward the mask pattern (13). The capillary (12) is distant from the substrate (11) as a predetermined distance, wherein the bottom end part (12a) toward the substrate has a pointed shape. As described above, any additive is added to the conductive polymer ink (10) to improve the spraying state and the electric conductivity.
As the conductive polymer materials, polyethylenedioxythiophene (PEDOT), polyacetylene, polypyrrole, polythiophene, polyaniline and the like and preferably polyethylenedioxythiophene polystyrenesul fonate (PEDOT:PSS) may be used. However, the present invention is not surely limited to these materials, but any polymer material having transparency and electric conductivity may be applied. As the additive, for example, polyalcohol such as glycerol or sorbitol is used.
An electrode (15) is inserted at the top of the capillary (12) and placed inside the conductive polymer ink (10). The electrode (15) is connected to a first power source (16a) which may apply high voltage. Optionally, a gas injecting tube (17) may be further connected to the top of the capillary (12) to increase spray efficiency, on jetting the conductive polymer ink (10).
In addition, a guide ring (18a) may be further instal led near to the bottom end part (12a) of the capillary (12), and a collimating electrode (18b) and a Teflon sheet (18c) may be further installed at the upper of the mask pattern (13). The guide ring (18a) and the collimating electrode (18b) are connected to a second power source (16b), which serve for the conductive polymer ink (10) jetted from the capillary (12) to be controlled toward the substrate (11). The Teflon sheet (18c) is a shielding screen prevent ing the jetted conductive polymer ink (10) or particles (10a) from escaping outside.
If high voltage is applied to the conductive polymer ink (10) via the electrode (15) from the first power source (16a) in a state that the substrate holder (14) is grounded, the electrostatic spray printing process is carried out by the principle described above. That is, the conductive polymer ink (10) is sprayed from the capillary (12), with concentrating electric field at the bottom end part (12a) of the capillary (12), and the sprayed conductive polymer ink (10) is induced toward the substrate (11) by the electrostatic force. The conductive polymer ink (10) is laminated on the substrate (11) in a form of very small particles. Therefore, the conductive polymer particles (10a) are laminated on the specific surface area of the substrate (11) exposed to the outside of the mask pattern (13) to form the transparent electrode.
Subsequently, the transparent electrode is sufficiently dried, to prevent a defect such as a pinhole from being developed and improve its optical properties. This step may be, for example, carrying out a process of thermally hardening at about 180°C or less for several tens minutes.
During carrying out the electrostatic spray printing process by applying high voltage to the conductive polymer ink, voltage may be separately applied to the guide ring (18a) and the collimating electrode (18b) via the second power source (16b) and the substrate (11) maybe rotated via the substrate holder (14). These contribute to improve uniformity and denseness of the transparent electrode. However, these may be optionally selected. Through voltage is not applied via the second power source (16b) or the substrate holder (14) is not rotated, the electrostatic spray printing method according to the present invention may greatly improve film uniformity and denseness of the transparent electrode over the existing spin coating.
To show electrical properties of the transparent electrode fabricated by the method described above, an experiment was practiced. The experimental example of the present invention is explained below.
First, a general OHP film was used as the substrate, and PEDOT÷PSS and glycerol were mixed in a ratio of 10:6, respectively, and used as the conductive polymer material and the additive. Specifically, as the conductive polymer material, Baytron PH 500 product from H. C. Starck company was used. The high voltage applied via the first power source was 7 kV, and no voltage was applied via the second power source. The time of vapor depositing is two hours, and then a drying process was carried out at 120°C for 30 minutes.
In comparison, the transparent electrode was fabricated by using the existing spin coating from the same substrate and conductive polymer material as above. It was as a process condition of the spin coating to rotate at 500 rpm for 10 seconds and then at 1000 rpm for 15 seconds. The condition of drying was the same.
An electrical property assay was to measure each sheet resistance of the transparent electrodes using the known 4-point probe system. As a result, in case of the comparative example for spin coating, the values of sheet resistance were not uniform as 90 Ω/O to several kΩ/rj. However, in case of the experimental example for the present invention, the values of sheet resistance were uniform as 24Ω/D, 27Ω/G, 40Ω/D, and 27Ω/D, and the average value was only 30Ω/D.
Figs. 3 and 4 are plane and section photographs of the conductive polymer transparent electrode according to experimental examples of the present invention. Referring to Fig. 3, root-mean-square (RMS) roughness of the transparent electrode was only about 4.6 nm. Referring to Fig. 4, it could be known that thickness of the transparent electrode was about 650 nm. Therefore, it could be known that the conductive polymer transparent electrode of the present invention had very excellent uniformity.
The conduct ive polymer transparent electrode and the method of fabr icat ing the same were explained above via examples. In the specification and drawings, the preferred embodiments of the present invention were disclosed. Although specific terms were used, these are used only as general meanings, to easily explain the technical context of the present invention and promote understand the present invention, which are not intended to limit the scope of the present invention. In addition to the embodiments disclosed herein, it will be apparent to those skilled in the technical field, to which the present invent ion pertains, that any modified example based on the technical idea of the present invention can be practiced. [Industrial Applicability]
Since the present invention provides a method of fabricating a transparent electrode by using conductive polymer materials instead of the existing metal oxides, it may solve the problem of the metal oxide transparent electrodes, and the electrostatic spray printing method, wherein the conductive polymer particles are laminated on the substrate, has an advantage that the transparent electrode may be easily fabricated on even a plastic substrate. In addition, the conductive polymer transparent electrode fabricated by the fabricating method according to the present invention does not only have very excellent film uniformity and denseness, but also exhibit excellent property enough to compete with the existing metal oxide transparent electrodes, even in terms of electric conductivity, since the conductive polymer materials are laminated on the substrate, with having electrostatic force.

Claims

[CLAIMS] [Claim 1]
A method of fabricating a conductive polymer transparent electrode comprising steps of placing a substrate on a substrate holder; filling a conductive polymer ink into a capillary, which is placed upward said substrate; applying voltage in said conductive polymer ink within said capillary, in a state that said substrate holder is grounded; and inducing said conductive ink toward said substrate, so that said conductive polymer particles are laminated on a surface of said substrate to form the transparent electrode, wherein said conductive polymer ink is sprayed from said capillary, with concentrating electric field at the end of said capil lary. [Claim 2]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized by further comprising a step of forming a mask pattern on the surface of said substrate, wherein said conductive polymer particles in sad step of forming the transparent electrode are laminated on the surface of said substrate exposed to outside in said mask pattern. [Claim 3]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized in that said conductive polymer particle is polyethylenedioxythiophene polystyrenesulfonate. [Claim 4]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized in that said conductive polymer particle is one selected from polyethylenedioxythiophene, polyacetylene, polypyrrole, polythiophene and polyaniline. [Claim 5]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized in that said additive is polyalcohol. [Claim 6]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized in that said substrate is a plastic substrate. [Claim 7]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized in that said step of forming the transparent substrate is carried out in a state that said substrate holder is rotated. [Claim 8]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized by further comprising a step of installing a guide ring near to the lower end of said capi 1 lary for said conductive polymer ink to be controlled toward said substrate and forming a collimating electrode on the top of said substrate. [Claim 9]
The method of fabricating a conductive polymer transparent electrode according to Claim 1, characterized by further comprising a step of thermally hardening said transparent electrode at about 180 °C or less. [Claim 10]
A conductive polymer transparent electrode fabricated by the method of fabricating according to any one of Claims 1 to 9.
PCT/KR2008/002236 2008-04-21 2008-04-21 Conductive polymer transparent electrode and fabricating method thereof WO2009131257A1 (en)

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