TW200939486A - Method of patterning TCO (transparent conductive oxide) of a conductive glass and conductive glass prepared thereby - Google Patents

Method of patterning TCO (transparent conductive oxide) of a conductive glass and conductive glass prepared thereby Download PDF

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Publication number
TW200939486A
TW200939486A TW97150044A TW97150044A TW200939486A TW 200939486 A TW200939486 A TW 200939486A TW 97150044 A TW97150044 A TW 97150044A TW 97150044 A TW97150044 A TW 97150044A TW 200939486 A TW200939486 A TW 200939486A
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TW
Taiwan
Prior art keywords
transparent conductive
electrode
glass
glass substrate
oxide film
Prior art date
Application number
TW97150044A
Other languages
Chinese (zh)
Other versions
TWI473276B (en
Inventor
Ho-Gi Bae
Jong-Bok Kim
Hyoung-Don Moon
Tae-Jin Park
Original Assignee
Dongjin Semichem Co Ltd
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Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of TW200939486A publication Critical patent/TW200939486A/en
Application granted granted Critical
Publication of TWI473276B publication Critical patent/TWI473276B/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2081—Serial interconnection of cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Electromagnetism (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Materials Engineering (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The present invention relates to a method of patterning a transparent conductive oxide film of conductive glass, and a conductive glass prepared thereby. Specifically, the present invention relates to a method of patterning a transparent conductive oxide film of a conductive glass comprising the steps of: forming a photoresist pattern on the part of the surface of a glass substrate where a transparent conductive oxide film is not to be formed; forming a transparent conductive film on the glass substrate; and removing the photoresist from the glass substrate, and a conductive glass prepared thereby. According to the present invention, a transparent conductive oxide (TCO) film can be patterned more easily and more inexpensively. Particularly, in the case of using TCO consisting of FTO, a conductive glass comprising FTO pattern formed thereon can be manufactured without using expensive laser equipment, and such conductive glass can be used as an electrode plate of a dye-sensitized solar cell.

Description

200939486 六、發明說明： C發明所屬之技術領域】 發明領域 5 ❹ 10 15 ❹200939486 VI. Description of the invention: Technical field to which C invention belongs] Field of the invention 5 ❹ 10 15 ❹

本發明係有關一用於圖案化導電性破璃的透明導。 氧化物骐之方法及一藉其製備的導電性玻璃，更特别=性 一用於圖案化導電性玻璃的透明導電性氧化物骐之方關 其可更容易及更便宜地圖案化一TC〇(透明導電性氣化物 膜’且特別在使用由FTO組成的TCO之案例中，不使用） 貴的雷射設備即可製造出一其上形成有FTO圖案之導 P 子^性 玻璃’其可用來作為一染料敏化太陽能電池的—電極板 以及一藉其製備的導電性玻璃。The present invention relates to a transparent guide for patterning conductive glass. The method of oxide bismuth and the conductive glass prepared by the same, more particularly, the transparent conductive oxide used for patterning the conductive glass, which can more easily and cheaply pattern a TC 〇 (Transparent Conductive Gasification Membrane' and especially in the case of using TCO composed of FTO, not used) Explosive laser equipment can produce a P-type glass on which an FTO pattern is formed. It is used as an electrode plate for a dye-sensitized solar cell and a conductive glass prepared therefrom.

【先前技術：J 發明背景 一般而言’對於供顯示器用的透明導電性膜、供太陽 能電池用的透明導電性膜等係使用一透明導電性塗層，且 市場日益擴大。一般藉由將導電性材料塗覆於一電性絕緣 體玻璃（裸玻璃，鹼石灰）上予以製備。 玻璃是一種在室溫具有從⑺-^至⑺-11 (Qcm)·1導電度之 電性絕緣體。為了對於玻璃絕緣體提供導電度同時維持高 的透射比(transmittance)，將TCO(透明導電性氧化物）或金 屬塗覆於玻璃表面上以形成一透明導電性塗層且藉此製備 一導電性玻璃。 然而，一導電性玻璃的透明導電性塗層未必塗覆於整 體玻璃表面上。一般而言，根據應用領域或設備來形成適 20 200939486 當的圖案（移除一部份且維持其餘部份）。譬如，參照第1圖 所示的染料敏化太陽能電池，使用一包含分別塗覆有作為 透明導電性塗層之TCO的一上電極（第二電極）及一下電極 (第一電極)之導電性玻璃，且TCO被圖案化藉以具有由第1 5 圖的圓形表示之經切割部份。 為了圖案化一導電性玻璃上的透明導電性塗層，通常 在TCO置於整體基材上之時形成圖案，且因此利用pR來 ’ 曝光一罩幕上所形成的影像並使PR顯影，然後，利用一蝕 刻劑作蝕刻以形成一電路圖案。然而，為了製造染料敏化 © 10 太陽能電池，FTO因為在近似500至6〇(rc高溫下呈熱性穩 定且具有優良抗化學性因此可承受電解質，所以主要用來 作為TCO，並且，在使用一可在低溫作處理的材料之案例 中偶而使用ITO，雖然其光電轉換效率很低。 使用ITO的案例中，利用蝕刻劑作蝕刻形成一圖案。然 15 而，使用曝光及蝕刻劑之化學蝕刻的問題係在於：使用蝕刻 劑導致成本增加，製程並不容易，且很可能造成環境污染。 使用FTO的案例中’因為!^〇的優良抗化學性導致無法 — 執行使用蝕刻劑的化學蝕刻，應如第2圖所示利用雷射形成 電路圖案’其增高設備成本且降低生產力。 20 因此，亟需發展出一當利用TCO在製備一其上形成有 一圖案之導電性玻璃時並不使用既有採用電路圖案化的曝 光的雷射圖案或化學蝕刻來圖案化TCO之方法。 【内^§1】 揭不 4 200939486 技術問題 為了解決習知技術的上述問題，本發明之一目的係提 供一用於_化朗導紐氧化物狀方法，其可更容易 及更便利地圖案化了⑺’且特別是在使用由打〇組成的 5 ❹ 10 15 Ο 之案例中’不使用昂貴的㈣設備即可製造-其上形成有 FTO圖案之導電性玻璃，該導電性玻璃用來作為一染料敏 化太陽能電池的-電極板，以及—藉其製備之導電性玻璃。 技術解決方案 為了達成該目的，本發明提供一圖案化導電性玻璃之 透明導魏氧化物朗方法，包含下列步驟：形成一光阻 圖案於其巾不欲形成—透明導電性氧化物膜之—玻璃基材 的表面部份上；形成—透明導電性膜於玻璃基材上；及自 玻璃基材移除光阻。 本發明亦提供一藉由本發明的方法所製備之一導電性 玻璃’包含一玻璃基材及一形成於該玻璃基材上之透明導 電性氧化物膜圖案。 本發明亦提供一染料敏化太陽能電池，包含：一第一 電極，其由透明電極組成；一第二電極，其組合至與透明 電極相對的表面；及—中間層，其包含第一與第二電極之 間的氧化物半導體、染料及電解質，其中第一電極或第二 電極包含本發明的導電性玻璃。 有利效應 根據本發明’可更容易及更便宜地圖案化一透明導電 性氧化物(TCO)膜。特別地，在使用由FT0組成的TCO之案 20 200939486 例中，不使用昂貴的雷射設備即可製造一其上形成有FTO 圖案之導電性玻璃，且此導電性玻璃可用來作為一染料敏 化太陽能電池的一電極板。 圖式簡單說明 5 第1圖為示意地顯示根據本發明的一實施例之一染料 敏化太陽能電池的橫剖視圖； 第2圖示意地顯示使用FOT作為一透明導電性塗層之 習知技術的一圖案化方法； 第3圖示意地顯示根據本發明的一實施例之一用於圖 10 案化導電性玻璃的透明導電性氧化物膜之方法。 t實施方式3 發明模式 現在將參照附圖詳細地說明本發明。 本發明係有關一圖案化導電性玻璃之透明導電性氧化 15 物膜的方法，其包含下列步驟：形成一光阻圖案於其中不 欲形成一透明導電性氧化物膜之一玻璃基材的表面部份 上；形成一透明導電性膜於玻璃基材表面上；及自玻璃基 材移除光阻。 第3圖顯示使用負光阻(PR)之根據本發明的方法之一 20 實施例。參照第3圖，負光阻施加至一玻璃基材，其上放置 有將被圖案化藉以只對於一其中留存有PR的部份（其中一 透明導電性氧化物膜不欲形成於該玻璃基材上）執行曝光 之光罩，且執行曝光以只在顯影後留下經曝光的PR，藉此 形成PR圖案（其中一透明導電性氧化物膜不欲形成於該玻 200939486 5 e 10 15 20 璃基材上之部份）。相反地，在使用正PR的案例中，可藉由 相反地設定經曝先部份來形成相同的PR圖案。負Pr較佳具 有逆反的推拔形狀藉以便利於PR的移除。然而，正Pr亦可 根據PR種類而具有逆反的推拔形狀。較佳形成一具有逆反 推拔形狀的橫剖面之PR圖案’因為其便利於PR的移除。只 要可獲得第3圖的第二步驟中之PR圖案、亦即只要可在一其 中一透明導電性氧化物膜不欲形成於該玻璃基材上之部份 上獲得一光阻圖案，則可使用任何製程。 確切來說，在形成一透明導電性氧化物(TC〇)膜所需要 之一裸玻璃（鹼石灰)上，施加用於形成一主要供顯示器用的 隔間之負PR，利用曝光罩幕來曝光所想要的電路形狀，然 後作顯影。因為tco的膜厚度概括對於ITO為1500至2〇〇 a 且對於FTO為6000至8000 A而因此介於近似1500至8000 A 之間，且隔間應該更高藉以能夠作圖案化，所以隔間的高 度車父佳為1〜3 μηι如第3圖所示。並且，隔間的高度取決於設 計值。 接著，在具有依此形成的PR圖案之玻璃基材上，形成 -透明導電性氧化物(TCG)膜。較佳藉由其巾使膜在玻璃基 材上自底部生長至頂部之異向性沉積來形成透明導電性氧 化物膜，因為其如第3圖所示只形成一透明導電性氧化物膜 於頂部上，故便利於PR及位於PR上的TC〇之移除。在如第 3圖所示於逆反推拔狀!^圖案上執行異向性沉積之案例 中’只在PR圖案頂部上執行沉積藉以便利於pR的移除。異 向性蝕刻係包括氣相沉積諸如CVD、濺鍍、濕蝕刻諸如喷 7 200939486 灑塗覆等。 在形成一透明導電性氧化物膜之製程中，玻璃基材較 佳被加熱到150至250°C、更佳被加熱到20〇°c。因為pr不需 要分離的固化製程，且可在形成一透明導電性氧化物膜的 5實際製程中自然地獲得此條件，故加熱到上述溫度範圍係 可簡化製程。因為在約2〇(TC的基材溫度執行利用CVD、濺 鍍、喷灑等形成一TCO膜之製程，用於隔間的.pR係被自 然地固化及硬化而不需要分離的固化製程。 可使用不同材料作為TCO，且就製程穩定度及製造容 10 易度來說偏好採用ITO或FTO。並且，在使用ITO或FTO的 案例中，較佳進一步在形成一透明導電性氧化物膜的步驟 與移除光阻的步驟之間包含使透明導電性氧化物膜退火之 步驟，如第3圖所示。一TC〇膜形成後藉由退火的熱處理係 可增加TCO膜的結晶性(cryStaiiinity) 〇退火並不限於ιτο及 15 FT0,而可選擇性施加至任何可藉由退火改良性質的TCO。 退火概括對於ITO在近似250至350。(：、而對於FTO在 500°C左右的溫度執行。在FTO的案例中，因為退火溫度充 分高於時常施用的PR之Td(分解溫度），PR會藉由退火被部 份地移除，故能夠在一短時間内作後續的PR移除。 2〇 接著，自玻璃基材移除PR’藉由該製程與PR —起移除 一沉積於PR上之透明導電性氧化物膜，因而獲得一如第3 圖底部所示具有圖案之導電性玻璃。確切來說，PR係利用 再製化學物（譬如，以胺為基礎的有機溶劑)移除，且執行清 洗以獲得一其上形成有電路形狀之TCO玻璃。 200939486 5 10 15 ❿ 本發明亦提供一具有藉由如上述用於圖案化導電性破 璃的透明導電性氧化物膜之方法所製備的透明導電性氧化 物膜圖案之導電性玻璃。本發明的導電性破璃係由如上述 用於圖案化導電性玻璃的透明導電性氧化物獏之方法所製 備，並包含-麵基材及—職於其上之透料電性氧化 物膜圖案，其範例顯示於第3圖的底部。 該導電性破璃可使用於顯示器、太陽能電池等。本發 明亦提供-包含科玻狀染料魏太 導電性玻璃包含-第—電極，其由透明電極組成；一第^ 電極，其組合至與透明電極相對之表面；及—中間層，^ 包含第-電極與第二電極之間的氧化物半導體（孽如了 ™2)、染料及電解質，其中第一電極或第二電極包 的導電性玻璃。 本發明的染料敏化太陽能電池之—實施例顯示於扪 圖。參照第旧，第—電極及第4極皆由本發明的導電性 玻璃構成。然而’只有第—電極或第二電極可由本發明的 導電性玻璃構成。 一般而言，一染料敏化太陽能電池包含一第一電極（第 1圖的下電極），一第二電極（第丨圖的上電極），一含有氧化 物半導體粒子（譬如Ti〇2)及染料之層，及一置於其上之電解 質層。第一電極可由本發明的導電性玻璃構成，而半導體 氧化物層（譬如Ti〇2)可形成於其上；或者，第二電極可由本 發明的導電性玻璃構成，且pt可塗覆於其底表面上。確切 來說’在一具有根據本發明的方法所形成的一圖案之玻璃 20 200939486 基材上，形成一身為染料敏化太陽能電池的基本結構之光 電極(Ti〇2)，且相對電極Pt形成於相對的基材（一第二電極) 上。染料被吸收至光電極中，且兩基材組合，然後將電解質 注射至内側’且密封住入口以獲得—染料敏化太陽能電池。 本發明不限於上述範例及附圖，且〆般熟習該技藝者 可作出不同修改或更改而不脫離如申請專利範圍所描述之 本發明的態樣與範圍。 產業利用性 根據本發明，可更容易且更便宜地圖案化一透明導電 © 10 性氧化物(TCO)膜。特別是在使用由FTO組成的TCO之案例 中，不使用昂貴的雷射設備即可製造出一其上形成有FT〇 圖案之導電性玻璃’且此導電性玻璃可用來作為一染料敏 化太陽能電池的一電極板。 . I：圖式簡單說明 15 第1圖為示意地顯示根據本發明的一實施例之一染料 敏化太陽能電池的橫剖視圖； ο 第2圖示意地顯示使用FOT作為一透明導電性塗層之 胃 習知技術的一圖案化方法； 第3圖示意地顯示根據本發明的一實施例之一用於圖 20 案化導電性玻璃的透明導電性氧化物膜之方法。 【主要元件符號說明】 (無） 10[Prior Art: J Background] Generally, a transparent conductive coating is used for a transparent conductive film for a display, a transparent conductive film for a solar cell, and the like, and the market is expanding. It is generally prepared by coating a conductive material on an electrically insulating glass (bare glass, soda lime). The glass is an electrical insulator having a conductivity of from (7) to from (7) to 11 (Qcm)·1 at room temperature. In order to provide electrical conductivity to the glass insulator while maintaining a high transmittance, a TCO (transparent conductive oxide) or metal is coated on the surface of the glass to form a transparent conductive coating and thereby prepare a conductive glass. . However, a transparent conductive coating of a conductive glass is not necessarily applied to the entire surface of the glass. In general, the pattern of the 200939486 is formed according to the application area or equipment (remove part and maintain the rest). For example, referring to the dye-sensitized solar cell shown in Fig. 1, conductivity of an upper electrode (second electrode) and a lower electrode (first electrode) each containing a TCO coated as a transparent conductive coating is used. The glass, and the TCO is patterned to have a cut portion represented by the circle of Figure 15. In order to pattern a transparent conductive coating on a conductive glass, a pattern is typically formed when the TCO is placed on the monolith substrate, and thus the image formed on a mask is exposed using pR and the PR is developed, and then An etchant is used for etching to form a circuit pattern. However, in order to manufacture a dye-sensitized © 10 solar cell, FTO is mainly used as a TCO because it is heat-stable at approximately 500 to 6 〇 (rc high temperature and has excellent chemical resistance, so it is mainly used as a TCO, and ITO can be used occasionally in the case of materials treated at low temperatures, although its photoelectric conversion efficiency is very low. In the case of ITO, an etchant is used for etching to form a pattern. However, chemical etching using an exposure and an etchant is used. The problem lies in the fact that the use of an etchant leads to an increase in cost, the process is not easy, and it is likely to cause environmental pollution. In the case of using FTO, 'because of the excellent chemical resistance of ^〇, it is impossible to perform chemical etching using an etchant, As shown in Fig. 2, the use of laser to form a circuit pattern 'increased equipment cost and reduced productivity. 20 Therefore, there is an urgent need to develop a conductive glass which is formed on a pattern by using TCO and does not use the existing one. A method of patterning a TCO using a circuit patterned exposed laser pattern or chemical etching. [内^§1] 揭不4 200939486 SUMMARY OF THE INVENTION In order to solve the above problems of the prior art, it is an object of the present invention to provide a method for forming a oxide-like oxide which can be more easily and conveniently patterned (7)' and especially in use. In the case of 5 ❹ 10 15 〇 composed of snoring, 'a manufacturing device can be manufactured without using expensive (four) equipment - an electroconductive glass on which an FTO pattern is formed, which is used as an electrode of a dye-sensitized solar cell A board, and a conductive glass prepared by the same. Technical Solution To achieve the object, the present invention provides a transparent conductive oxide oxide method for patterned conductive glass, comprising the steps of: forming a photoresist pattern on the towel thereof It is not desired to form a transparent conductive oxide film on the surface portion of the glass substrate; to form a transparent conductive film on the glass substrate; and to remove the photoresist from the glass substrate. The present invention also provides a The conductive glass of the invention comprises a glass substrate and a transparent conductive oxide film pattern formed on the glass substrate. The invention also provides a dye sensitization a solar cell comprising: a first electrode composed of a transparent electrode; a second electrode combined to a surface opposite to the transparent electrode; and - an intermediate layer comprising an oxide between the first electrode and the second electrode A semiconductor, a dye, and an electrolyte, wherein the first electrode or the second electrode comprises the conductive glass of the present invention. Advantageous Effects According to the present invention, a transparent conductive oxide (TCO) film can be more easily and inexpensively patterned. In the case of using TCO consisting of FT0, in the case of 200939486, a conductive glass on which an FTO pattern is formed can be produced without using expensive laser equipment, and the conductive glass can be used as a dye-sensitized solar energy. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing a dye-sensitized solar cell according to an embodiment of the present invention; and FIG. 2 is a view schematically showing the use of FOT as a transparent conductive coating. A patterning method of the prior art of the layer; FIG. 3 is a view schematically showing the transparent conductive oxygen used in the conductive glass of FIG. 10 according to one embodiment of the present invention. A method of forming a film. t. Embodiment Mode 3 The present invention will now be described in detail with reference to the accompanying drawings. The present invention relates to a method for patterning a transparent conductive oxide film of a conductive glass, comprising the steps of: forming a photoresist pattern on a surface of a glass substrate in which a transparent conductive oxide film is not desired to be formed. Forming a transparent conductive film on the surface of the glass substrate; and removing the photoresist from the glass substrate. Figure 3 shows an embodiment of a method according to the invention 20 using a negative photoresist (PR). Referring to FIG. 3, a negative photoresist is applied to a glass substrate on which a portion to be patterned is used so as to retain only a portion in which PR is left (a transparent conductive oxide film is not formed on the glass substrate). Exercising the reticle and performing exposure to leave the exposed PR only after development, thereby forming a PR pattern (wherein a transparent conductive oxide film is not intended to be formed on the glass 200939486 5 e 10 15 20 Part of the glass substrate). Conversely, in the case of using positive PR, the same PR pattern can be formed by setting the exposed portion instead. The negative Pr preferably has a reversed push-and-pull shape to facilitate the removal of the PR. However, positive Pr can also have a reversed push shape depending on the type of PR. It is preferable to form a PR pattern of a cross section having a reversed push-out shape because it facilitates the removal of the PR. As long as the PR pattern in the second step of FIG. 3 is obtained, that is, as long as a photoresist pattern can be obtained on a portion of the transparent conductive oxide film that is not desired to be formed on the glass substrate, Use any process. Specifically, on one of the bare glass (soda lime) required to form a transparent conductive oxide (TC〇) film, a negative PR for forming a spacer for the display is applied, using an exposure mask The desired circuit shape is exposed and then developed. Since the film thickness of tco is generally 1500 to 2 〇〇a for ITO and 6000 to 8000 A for FTO, so it is between approximately 1500 and 8000 A, and the compartment should be higher to be able to be patterned, so the compartment The height of the car is good for 1~3 μηι as shown in Figure 3. Also, the height of the compartment depends on the design value. Next, a transparent conductive oxide (TCG) film was formed on the glass substrate having the PR pattern thus formed. Preferably, the transparent conductive oxide film is formed by the epitaxial deposition of the film on the glass substrate from the bottom to the top by the towel, because it forms only a transparent conductive oxide film as shown in FIG. On the top, it facilitates the removal of the PR and the TC located on the PR. In the case where anisotropic deposition is performed on the reverse-removed pattern as shown in Fig. 3, deposition is performed only on the top of the PR pattern to facilitate the removal of pR. Anisotropic etching includes vapor deposition such as CVD, sputtering, wet etching such as spray 7 200939486 sprinkle coating, and the like. In the process of forming a transparent conductive oxide film, the glass substrate is preferably heated to 150 to 250 ° C, more preferably to 20 ° C. Since pr does not require a separate curing process and can be naturally obtained in the actual process of forming a transparent conductive oxide film, heating to the above temperature range simplifies the process. Since the process of forming a TCO film by CVD, sputtering, spraying, or the like is performed at a substrate temperature of about 2 Torr, the .pR system for the compartment is naturally cured and hardened without requiring a separate curing process. Different materials can be used as the TCO, and ITO or FTO is preferred in terms of process stability and manufacturing capacity. Moreover, in the case of using ITO or FTO, it is preferable to further form a transparent conductive oxide film. The step of annealing the transparent conductive oxide film is included between the step of removing the photoresist and the step of annealing the transparent conductive oxide film, as shown in Fig. 3. The crystallization of the TCO film can be increased by the annealing heat treatment after the formation of the TC film (cryStaiiinity) 〇 Annealing is not limited to ιτο and 15 FT0, but can be selectively applied to any TCO that can be modified by annealing. Annealing is generalized for ITO at approximately 250 to 350. (:, and for FTO at temperatures around 500 °C) Execution. In the case of FTO, since the annealing temperature is sufficiently higher than the Td (decomposition temperature) of the PR that is frequently applied, the PR is partially removed by annealing, so that subsequent PR removal can be performed in a short time. 2〇 Next, from the glass The material removal PR' is removed from the transparent conductive oxide film deposited on the PR by the process, thereby obtaining a patterned conductive glass as shown at the bottom of Fig. 3. Specifically, PR The removal is performed using a re-formed chemical (for example, an amine-based organic solvent), and cleaning is performed to obtain a TCO glass having a circuit shape formed thereon. 200939486 5 10 15 ❿ The present invention also provides a Conductive glass of a transparent conductive oxide film pattern prepared by a method for patterning a transparent conductive oxide film of conductive glass. The conductive glass of the present invention is used for patterning conductive glass as described above. The method of transparent conductive oxide yttrium is prepared, and comprises a - surface substrate and a dielectric oxide film pattern thereon, an example of which is shown at the bottom of Fig. 3. The conductive glass can be Used in displays, solar cells, etc. The present invention also provides - comprising a glassy dye, a Wei Tai conductive glass comprising - a first electrode, which is composed of a transparent electrode; and a second electrode, which is combined to be opposite to the transparent electrode a surface; and an intermediate layer, comprising an oxide semiconductor (such as TM2) between the first electrode and the second electrode, a dye, and an electrolyte, wherein the first electrode or the second electrode is coated with a conductive glass. The embodiment of the dye-sensitized solar cell is shown in the drawings. Referring to the first, the first electrode and the fourth electrode are all composed of the conductive glass of the present invention. However, only the first electrode or the second electrode can be electrically conductive by the present invention. Generally, a dye-sensitized solar cell comprises a first electrode (the lower electrode of FIG. 1), a second electrode (the upper electrode of the second figure), and an oxide semiconductor particle (such as Ti). 〇 2) and the layer of dye, and an electrolyte layer placed thereon. The first electrode may be composed of the conductive glass of the present invention, and a semiconductor oxide layer (such as Ti〇2) may be formed thereon; or the second electrode may be composed of the conductive glass of the present invention, and pt may be applied thereto On the bottom surface. Specifically, on a substrate 20 200939486 having a pattern formed by the method according to the present invention, a photoelectrode (Ti〇2) which is a basic structure of a dye-sensitized solar cell is formed, and the opposite electrode Pt is formed. On the opposite substrate (a second electrode). The dye is absorbed into the photoelectrode, and the two substrates are combined, and then the electrolyte is injected to the inside and the inlet is sealed to obtain a dye-sensitized solar cell. The invention is not limited to the above-described examples and the accompanying drawings, and various modifications and changes may be made without departing from the scope of the invention as described in the appended claims. Industrial Applicability According to the present invention, a transparent conductive © 10 oxide (TCO) film can be patterned more easily and cheaply. In particular, in the case of using a TCO composed of FTO, an electrically conductive glass having an FT〇 pattern formed thereon can be manufactured without using expensive laser equipment, and this conductive glass can be used as a dye-sensitized solar energy. An electrode plate of the battery. I: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing a dye-sensitized solar cell according to an embodiment of the present invention; ο FIG. 2 is a view schematically showing the use of FOT as a transparent conductive coating. A patterning method of the conventional technique of the stomach; Fig. 3 is a view schematically showing a method for the transparent conductive oxide film of the conductive glass of Fig. 20 according to an embodiment of the present invention. [Main component symbol description] (none) 10

Claims (1)

200939486 七 1. 、申請專利範圍： 導電性氧化物膜的方 種圖案化導電性破璃之透明 法，其包含下列步驟： 5 形成一光阻圖案於其中不欲形成一 化物膜之-玻璃基材的表面部份上； 透明導電性氧 形成一透明導電性臈於該玻璃基材上；及 自3玄玻璃基材移除該光阻。 2. e 10 如申請專利範圍第㈣之方法，其中該光阻圖案的橫刊 面為逆反的推拔形狀，且該透明導電性氧化物膜係由諸 如氣相沉積、濺鍍及嘴灑塗覆等異向性沉積所形成藉以 在該玻璃基材上自底部生長至頂部。 3.如申請專利範圍第1項之方法，其中在該形成一透明導 電性膜的步驟中，該玻璃基材被加熱到從15〇至25〇它之 一溫度。 15 4. 如申請專利範圍第1項之方法’其中該透明導電性膜係 為ITO或FTO，且該方法進一步在該形成一透明導電性 氧化物膜的步驟與該移除光阻的步驟之間包含退火該 透明導電性氧化物膜之步驟。 5. —種藉由申請專利範圍第1至4項中任一項之方法所製 備之導電性玻璃’其包含一玻璃基材及一形成於該玻璃 基材上之透明導電性氧化物膜圖案。 6. —種染料敏化太陽能電池，包含：一第—電極，其由一 透明電極組成；一第二電極，其組合至與該透明電極相 對之表面；及一中間層，其包含該等第一與第二電極之 20 200939486 間的氧化物半導體、染料、及電解質， 其中該第一電極或該第二電極包含申請專利範圍 第5項之導電性玻璃。200939486 VII. Patent application scope: A transparent method of patterning conductive thinning of a conductive oxide film, comprising the following steps: 5 forming a photoresist pattern in which a film is not formed - a glass base The surface portion of the material; transparent conductive oxygen forms a transparent conductive layer on the glass substrate; and the photoresist is removed from the 3 glass substrate. 2. e 10 The method of claim 4, wherein the horizontal cross-section of the photoresist pattern is a reverse-reduced push-out shape, and the transparent conductive oxide film is coated by, for example, vapor deposition, sputtering, and sprinkling. Anisotropic deposition is formed to grow from the bottom to the top on the glass substrate. 3. The method of claim 1, wherein in the step of forming a transparent conductive film, the glass substrate is heated to a temperature of from 15 Torr to 25 Torr. The method of claim 1, wherein the transparent conductive film is ITO or FTO, and the method further comprises the step of forming a transparent conductive oxide film and the step of removing the photoresist. The step of annealing the transparent conductive oxide film is included. 5. A conductive glass prepared by the method of any one of claims 1 to 4, which comprises a glass substrate and a transparent conductive oxide film pattern formed on the glass substrate . 6. A dye-sensitized solar cell comprising: a first electrode comprising a transparent electrode; a second electrode coupled to a surface opposite the transparent electrode; and an intermediate layer comprising the same An oxide semiconductor, a dye, and an electrolyte between 20 and 3939486 of the first electrode and the second electrode, wherein the first electrode or the second electrode comprises the conductive glass of claim 5th. 12 200939486 四、指定代表圖·· (一) 本案指定代表圖為：第（1 )圖。 (二) 本代表圖之元件符號簡單說明： (無) 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：12 200939486 IV. Designation of Representative Representatives (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW97150044A 2007-12-27 2008-12-22 Method of patterning tco(transparent conductive oxide) of a conductive glass and conductive glass prepared thereby TWI473276B (en)

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