TWI473276B - 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 PDFInfo
- Publication number
- TWI473276B TWI473276B TW97150044A TW97150044A TWI473276B TW I473276 B TWI473276 B TW I473276B TW 97150044 A TW97150044 A TW 97150044A TW 97150044 A TW97150044 A TW 97150044A TW I473276 B TWI473276 B TW I473276B
- Authority
- TW
- Taiwan
- Prior art keywords
- transparent conductive
- glass
- tco
- conductive oxide
- oxide film
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims description 76
- 238000000034 method Methods 0.000 title claims description 27
- 238000000059 patterning Methods 0.000 title claims description 15
- 229920002120 photoresistant polymer Polymers 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (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)
Description
本發明係有關一用於圖案化導電性玻璃的透明導電性氧化物膜之方法及一藉其製備的導電性玻璃，更特別有關一用於圖案化導電性玻璃的透明導電性氧化物膜之方法，其可更容易及更便宜地圖案化一TCO(透明導電性氧化物)膜，且特別在使用由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FTO圖案之導電性玻璃，其可用來作為一染料敏化太陽能電池的一電極板，以及一藉其製備的導電性玻璃。 The present invention relates to a method for patterning a transparent conductive oxide film of a conductive glass and a conductive glass prepared thereby, and more particularly to a transparent conductive oxide film for patterning a conductive glass. A method which can more easily and cheaply pattern a TCO (Transparent Conductive Oxide) film, and particularly in the case of using a TCO composed of FTO, can be manufactured without using expensive laser equipment An electroconductive glass formed with an FTO pattern which can be used as an electrode plate of a dye-sensitized solar cell, and a conductive glass prepared therefrom.
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。 In general, a transparent conductive coating for a transparent conductive film for a display, a transparent conductive film for a solar cell, or the like is used, and the market is expanding. It is generally prepared by coating a conductive material on an electrical insulator glass (bare glass, soda lime).
玻璃是一種在室溫具有從10-10至10-11(Ωcm)-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。 Glass is an electrical insulator having a conductivity of from 10 -10 to 10 -11 (Ωcm) -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. .
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 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 11、11’的一上電極16’(第二電極)及一下電極16(第一電極)之導電性玻璃，且TCO被圖案化藉以具有由第1圖的圓形表示之經切割部份。 However, a transparent conductive coating of a conductive glass is not necessarily applied to the entire glass surface. In general, depending on the application area or equipment The pattern (remove a portion and maintain the rest). For example, referring to the dye-sensitized solar cell shown in Fig. 1, an upper electrode 16' (second electrode) and a lower electrode 16 each containing a TCO 11, 11' as a transparent conductive coating are used. The conductive glass of the first electrode), and the TCO is patterned to have a cut portion represented by a circle of FIG.
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，為了製造染料敏化太陽能電池，FTO因為在近似500至600℃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。 In order to pattern a transparent conductive coating on a conductive glass, a pattern is usually formed when the TCO is placed on the entire substrate, and thus, the image formed on a mask is exposed by PR and the PR is developed, and then An etchant is used for etching to form a circuit pattern. However, in order to manufacture dye-sensitized solar cells, FTO is mainly used as a TCO because it is thermally stable at a high temperature of approximately 500 to 600 ° C and has excellent chemical resistance, so it can be used as a TCO at a low temperature. In the case of treated materials, ITO was occasionally used, although its photoelectric conversion efficiency was low.
使用ITO的案例中，利用蝕刻劑作蝕刻形成一圖案。然而，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。 In the case of using ITO, an etchant is used for etching to form a pattern. However, the problem of chemical etching using an exposure and an etchant is that the use of an etchant results in an increase in cost, a process is not easy, and it is likely to cause environmental pollution.
使用FTO的案例中，因為FTO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。 In the case of using FTO, since the chemical resistance of the etchant cannot be performed because of the excellent chemical resistance of the FTO, the circuit pattern should be formed by using laser as shown in Fig. 2, which increases equipment cost and reduces productivity.
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。 Therefore, there is a need to develop a method of patterning a TCO without using an exposed laser pattern or chemical etching using circuit patterning when using TCO to prepare a conductive glass on which a pattern is formed.
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圖案化透明導電性氧化物膜之方法，其可更容易及更便利地圖案化TCO，且特別是在使用由FTO組成的TCO之案例中，不使用昂貴的雷射設備即可製造一其上形成有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一電極板，以及一藉其製備之導電性玻璃。 In order to solve the above problems of the prior art, it is an object of the present invention to provide a method for patterning a transparent conductive oxide film which can more easily and conveniently pattern TCO, and in particular, is composed of FTO In the case of TCO, a conductive glass on which an FTO pattern is formed can be fabricated without using expensive laser equipment, and the conductive glass is used as an electrode plate of a dye-sensitized solar cell, and Prepared conductive glass.
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電性氧化物膜的方法，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；形成一透明導電性氧化物膜於玻璃基材上；及自玻璃基材移除光阻。 In order to achieve the object, the present invention provides a method of patterning a transparent conductive oxide film of a conductive glass, comprising the steps of: forming a photoresist pattern in which a glass substrate of a transparent conductive oxide film is not formed. Forming a transparent conductive oxide film on the glass substrate; and removing the photoresist from the glass substrate.
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。 The invention also provides a conductive glass prepared by the method of the invention comprising a glass substrate and a transparent conductive oxide film pattern formed on the glass substrate.
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；及一中間層，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。 The present invention also provides a dye-sensitized 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 including the first and the first An oxide semiconductor, a dye, and an electrolyte between the two electrodes, wherein the first electrode or the second electrode comprises the conductive glass of the present invention.
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FTO組成的TCO之案 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。 According to the present invention, a transparent conductive oxide (TCO) film can be patterned more easily and cheaply. In particular, in the case of using a TCO consisting of FTO In the example, a conductive glass on which an FTO pattern is formed can be manufactured without using an expensive laser device, and the conductive glass can be used as an electrode plate of a dye-sensitized solar cell.
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案化導電性玻璃的透明導電性氧化物膜之方法。 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 a patterning method using a conventional technique of using FOT as a transparent conductive coating; Fig. 3 is a view schematically showing a method for patterning a transparent conductive oxide film of a conductive glass according to an embodiment of the present invention.
現在將參照附圖詳細地說明本發明。 The invention will now be described in detail with reference to the accompanying drawings.
本發明係有關一圖案化導電性玻璃之透明導電性氧化物膜的方法，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；形成一透明導電性氧化物膜於玻璃基材表面上；及自玻璃基材移除光阻。 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 in a surface portion of a glass substrate in which a transparent conductive oxide film is not desired to be formed. Forming a transparent conductive oxide film on the surface of the glass substrate; and removing the photoresist from the glass substrate.
第3圖顯示使用負光阻(PR)31之根據本發明的方法之一實施例。參照第3圖，負光阻31施加至一玻璃基材30，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32，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34(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)。相反地，在使用正PR的案例中，可藉由相反地設定經曝光部份來形成相同的PR圖案。負PR較佳具有倒錐形藉以便利於PR的移除。然而，正PR亦可根據PR種類而具有倒錐形。較佳形成一具有倒錐形的橫剖面之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34、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。 Figure 3 shows an embodiment of the method according to the invention using a negative photoresist (PR) 31. Referring to FIG. 3, a negative photoresist 31 is applied to a glass substrate 30 on which a portion to be patterned is applied so as to retain only a portion in which PR is left (in which a transparent conductive oxide film is not intended to be formed) The reticle 32 is exposed on the glass substrate, and exposure is performed to leave the exposed PR only after development, thereby forming the PR pattern 34 (wherein a transparent conductive oxide film is not desired) Part of the glass substrate). Conversely, in the case of using positive PR, the same PR pattern can be formed by setting the exposed portions in reverse. The negative PR preferably has an inverted cone to facilitate the removal of the PR. However, the positive PR may have an inverted cone depending on the type of PR. It is preferred to form a PR pattern having a reverse tapered cross section because it facilitates the removal of the PR. As long as the PR pattern 34 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, Any process can be used.
確切來說，在形成一透明導電性氧化物(TCO)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200Å且對於FTO為6000至8000Å而因此介於近似1500至8000Å之間，且隔間應該更高藉以能夠作圖案化，所以隔間的高度33較佳為1~3μm如第3圖所示。並且，隔間的高度取決於設計值。 Specifically, a negative PR for forming a spacer for the display is applied to one of the bare glass (soda lime) required to form a transparent conductive oxide (TCO) film, and is exposed by an exposure mask. The desired circuit shape is then developed. Since the film thickness of the TCO is generally 1500 to 200 Å for ITO and 6000 to 8000 Å for FTO, and thus between approximately 1500 and 8000 Å, and the compartment should be higher to be patterned, the height 33 of the compartment is preferred. It is 1~3μm as shown in Figure 3. Also, the height of the compartment depends on the design value.
接著，在具有依此形成的PR圖案之玻璃基材上，形成一透明導電性氧化物(TCO)膜。較佳藉由其中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35，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TCO之移除。在如第3圖所示於倒錐形PR圖案34上執行異向性沉積之案例中，只在PR圖案34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 噴灑塗覆等。 Next, a transparent conductive oxide (TCO) film was formed on the glass substrate having the PR pattern thus formed. The transparent conductive oxide film 35 is preferably formed by anisotropic deposition in which the film is grown from the bottom to the top on the glass substrate 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 TCO located on the PR. In the case where anisotropic deposition is performed on the inverted tapered PR pattern 34 as shown in FIG. 3, deposition is performed only on the top of the PR pattern 34 to facilitate the removal of the PR. Anisotropic etching includes vapor deposition such as CVD, sputtering, wet etching such as Spray coating, etc.
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℃、更佳被加熱到200℃。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200℃的基材溫度執行利用CVD、濺鍍、噴灑等形成一TCO膜之製程，用於隔間的負PR係被自然地固化及硬化而不需要分離的固化製程。 In the process of forming a transparent conductive oxide film, the glass substrate is preferably heated to 150 to 250 ° C, more preferably to 200 ° C. Since PR does not require a separate curing process, and this condition can be naturally obtained in an actual process for 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 200 ° C, the negative PR system for the compartment is naturally cured and hardened without requiring a separate curing process.
可使用不同材料作為TCO，且就製程穩定度及製造容易度來說偏好採用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TCO膜形成後藉由退火的熱處理係可增加TCO膜的結晶性(crystallinity)。退火並不限於ITO及FTO，而可選擇性施加至任何可藉由退火改良性質的TCO。 Different materials can be used as the TCO, and ITO or FTO is preferred for process stability and ease of manufacture. Further, in the case of using ITO or FTO, it is preferable to further include a step of annealing the transparent conductive oxide film between the step of forming a transparent conductive oxide film and the step of removing the photoresist, as shown in FIG. Shown. The crystallinity of the TCO film can be increased by heat treatment after annealing of a TCO film. Annealing is not limited to ITO and FTO, but can be selectively applied to any TCO that can be modified by annealing.
退火概括對於ITO在近似250至350℃、而對於FTO在500℃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，故能夠在一短時間內作後續的PR移除。 Annealing is generally performed for ITO at approximately 250 to 350 °C and for FTO at temperatures around 500 °C. In the case of FTO, since the annealing temperature is sufficiently higher than the Td (decomposition temperature) of the PR which is frequently applied, the PR is partially removed by annealing, so that subsequent PR removal can be performed in a short time.
接著，自玻璃基材移除PR，藉由該製程與PR一起移除一沉積於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36。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。 Next, the PR is removed from the glass substrate, and the transparent conductive oxide film deposited on the PR is removed together with the PR by the process, thereby obtaining a patterned conductive glass 36 as shown at the bottom of FIG. Specifically, the PR is removed using a re-formed chemical (for example, an amine-based organic solvent), and cleaning is performed to obtain a TCO glass on which a circuit shape is formed.
本發明亦提供一具有藉由如上述用於圖案化導電性玻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。本發明的導電性玻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膜之方法所製備，並包含一玻璃基材及一形成於其上之透明導電性氧化物膜圖案，其範例顯示於第3圖的底部。 The present invention also provides a conductive glass having a transparent conductive oxide film pattern prepared by the method for patterning a transparent conductive oxide film of a conductive glass as described above. The conductive glass of the present invention is prepared by the above method for patterning a transparent conductive oxide film of a conductive glass, and comprises a glass substrate and a transparent conductive oxide film pattern formed thereon. An example of this is shown at the bottom of Figure 3.
該導電性玻璃可使用於顯示器、太陽能電池等。本發明亦提供一包含該導電性玻璃之染料敏化太陽能電池，該導電性玻璃包含一第一電極，其由透明電極組成；一第二電極，其組合至與透明電極相對之表面；及一中間層，其包含第一電極與第二電極之間的氧化物半導體(譬如，TiO2)、染料及電解質，其中第一電極或第二電極包含上述的導電性玻璃。 The conductive glass can be used for displays, solar cells, and the like. The present invention also provides a dye-sensitized solar cell comprising the conductive glass, the conductive glass comprising a first electrode composed of a transparent electrode; a second electrode combined to a surface opposite to the transparent electrode; An intermediate layer comprising an oxide semiconductor (eg, TiO 2 ), a dye, and an electrolyte between the first electrode and the second electrode, wherein the first electrode or the second electrode comprises the above-described conductive glass.
本發明的染料敏化太陽能電池之一實施例顯示於第1圖。參照第1圖，第一電極及第二電極皆由本發明的導電性玻璃構成。然而，只有第一電極或第二電極可由本發明的導電性玻璃構成。 An embodiment of the dye-sensitized solar cell of the present invention is shown in Fig. 1. Referring to Fig. 1, the first electrode and the second electrode are each composed of the conductive glass of the present invention. However, only the first electrode or the second electrode may be composed of the conductive glass of the present invention.
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16)，一第二電極(第1圖的上電極16’)，一含有氧化物半導體粒子(譬如TiO2)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TiO2)13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(12)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(TiO2)，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內側，且密封住入口以獲得一染料敏化太陽能電池。 In general, a dye-sensitized solar cell comprises a first electrode (the lower electrode 16 of FIG. 1), a second electrode (the upper electrode 16' of FIG. 1), and an oxide semiconductor particle (such as TiO 2 ). And a 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 TiO 2 ) 13 may be formed thereon; or the second electrode may be composed of the conductive glass of the present invention, and Pt (12) may be coated. Covered on the bottom surface. Specifically, on a glass substrate having a pattern formed by the method according to the present invention, a photoelectrode (TiO 2 ) which is a basic structure of a dye-sensitized solar cell is formed, and the opposite electrode Pt is formed in the opposite direction. On the 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.
本發明不限於上述範例及附圖，且一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。 The present invention is not limited to the above-described examples and the accompanying drawings, and various modifications and changes can be made without departing from the scope of the invention as described in the appended claims.
根據本發明，可更容易且更便宜地圖案化一透明導電性氧化物(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。 According to the present invention, a transparent conductive oxide (TCO) film can be patterned more easily and cheaply. Particularly in the case of using a TCO composed of FTO, a conductive glass on which an FTO pattern is formed can be manufactured without using an expensive laser device, and the conductive glass can be used as a dye-sensitized solar cell. An electrode plate.
10,10’,20‧‧‧裸玻璃 10,10’,20‧‧n bare glass
11,11’‧‧‧TCO 11,11’‧‧‧TCO
12‧‧‧Pt 12‧‧‧Pt
13‧‧‧TiO2 13‧‧‧TiO2
14‧‧‧玻璃熔料膏 14‧‧‧ glass frit paste
15‧‧‧Ag膏 15‧‧‧Ag paste
16‧‧‧下電極(第一電極) 16‧‧‧ lower electrode (first electrode)
16’‧‧‧上電極(第二電極) 16'‧‧‧Upper electrode (second electrode)
21‧‧‧FTO 21‧‧‧FTO
30‧‧‧鹼石灰裸玻璃；玻璃基板 30‧‧‧ Soda lime bare glass; glass substrate
31‧‧‧負光阻 31‧‧‧negative photoresist
32‧‧‧圖案狀光罩 32‧‧‧patterned mask
33‧‧‧隔間高度 33‧‧‧ Compartment height
34‧‧‧PR圖案 34‧‧‧PR pattern
35‧‧‧TCO 35‧‧‧TCO
36‧‧‧具有圖案之導電性玻璃 36‧‧‧patterned conductive glass
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案化導電性玻璃的透明導電性氧化物膜之方法。 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 a patterning method using a conventional technique of using FOT as a transparent conductive coating; Fig. 3 is a view schematically showing a method for patterning a transparent conductive oxide film of a conductive glass according to an embodiment of the present invention.
10,10’‧‧‧裸玻璃 10,10’‧‧‧Naked glass
11,11’‧‧‧TCO 11,11’‧‧‧TCO
12‧‧‧Pt 12‧‧‧Pt
13‧‧‧TiO2 13‧‧‧TiO2
14‧‧‧玻璃熔料膏 14‧‧‧ glass frit paste
15‧‧‧Ag膏 15‧‧‧Ag paste
16‧‧‧下電極(第一電極) 16‧‧‧ lower electrode (first electrode)
16’‧‧‧上電極(第二電極) 16'‧‧‧Upper electrode (second electrode)
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070138344A KR101446910B1 (en) | 2007-12-27 | 2007-12-27 | Method of patterning tco(transparent conductive oxide) of a conductive glass and conductive glass prepared thereby |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200939486A TW200939486A (en) | 2009-09-16 |
| TWI473276B true TWI473276B (en) | 2015-02-11 |
Family
ID=40824873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW97150044A TWI473276B (en) | 2007-12-27 | 2008-12-22 | Method of patterning tco(transparent conductive oxide) of a conductive glass and conductive glass prepared thereby |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101446910B1 (en) |
| TW (1) | TWI473276B (en) |
| WO (1) | WO2009084850A2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417318B (en) | 2011-07-28 | 2013-12-01 | Ind Tech Res Inst | Polyimide copolymers and method for fabricating patterned metal oxide layers |
| TWI523073B (en) | 2012-07-31 | 2016-02-21 | 財團法人工業技術研究院 | Patterning process for oxide film |
| KR102247767B1 (en) * | 2019-12-31 | 2021-05-03 | 포항공과대학교 산학협력단 | Silicon carbide trench mosfet with uniform thickness of trench oxidation layer and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654128A (en) * | 1994-10-21 | 1997-08-05 | Ngk Insulators, Ltd. | Single resist layer lift-off process for forming patterned layers on a substrate |
| US20040251508A1 (en) * | 2002-04-11 | 2004-12-16 | Takashi Tomita | Sensitizing dye solar cell |
| KR100773147B1 (en) * | 2007-04-27 | 2007-11-02 | 전남대학교산학협력단 | Dye-sensitized solar cell containing fluorescent material and method for manufacturing thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405658A (en) * | 1982-03-26 | 1983-09-20 | Sperry Corporation | Method of producing positive slope step changes on vacuum deposited layers |
-
2007
- 2007-12-27 KR KR1020070138344A patent/KR101446910B1/en active IP Right Grant
-
2008
- 2008-12-22 TW TW97150044A patent/TWI473276B/en not_active IP Right Cessation
- 2008-12-24 WO PCT/KR2008/007632 patent/WO2009084850A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654128A (en) * | 1994-10-21 | 1997-08-05 | Ngk Insulators, Ltd. | Single resist layer lift-off process for forming patterned layers on a substrate |
| US20040251508A1 (en) * | 2002-04-11 | 2004-12-16 | Takashi Tomita | Sensitizing dye solar cell |
| KR100773147B1 (en) * | 2007-04-27 | 2007-11-02 | 전남대학교산학협력단 | Dye-sensitized solar cell containing fluorescent material and method for manufacturing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009084850A3 (en) | 2009-11-05 |
| TW200939486A (en) | 2009-09-16 |
| WO2009084850A2 (en) | 2009-07-09 |
| KR101446910B1 (en) | 2014-10-06 |
| KR20090070358A (en) | 2009-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106782769A (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| CN102655146A (en) | Array substrate, array substrate preparation method and display device | |
| TWI473276B (en) | Method of patterning tco(transparent conductive oxide) of a conductive glass and conductive glass prepared thereby | |
| CN104411103B (en) | Manufacturing method of graphical thick film silver paste conducting layer | |
| JP2013539235A5 (en) | ||
| More et al. | Effect of Cleaning Process of Substrate on the Efficiency of the DSSC | |
| JP6222218B2 (en) | Thin film transfer method, thin film transistor manufacturing method, and pixel electrode forming method for liquid crystal display device | |
| CN102732879A (en) | Preparation method of titanium-dioxide-base conducting film | |
| KR20190099903A (en) | Method of patterning a hybrid transparent electrode | |
| CN107342229A (en) | A kind of noncrystal membrane device and preparation method | |
| CN109879277A (en) | A kind of graphene cleaning transfer method | |
| JP2006083036A (en) | Glass etching method, manufacturing method of transparent conductive substrate and photoelectric transducer | |
| CN113140679B (en) | Perovskite battery, preparation method thereof and preparation method of modification layer of perovskite battery | |
| TWI739190B (en) | Transparent organic solar cell module with patterned electrodes and manufacturing method thereof | |
| CN107359212A (en) | Electrically conducting transparent substrate, its preparation method and solar cell | |
| KR101383488B1 (en) | High Quality Flexible Transparent Electrodes and Fabricating Method Thereof | |
| KR101903187B1 (en) | Conductor plate and its manufacturing method | |
| KR101615288B1 (en) | Manufacturing method of the device for converting energy | |
| JP6284138B2 (en) | Dye-sensitized solar cell and method for producing the same | |
| JP3653762B2 (en) | Flat lens array and manufacturing method thereof | |
| KR101131005B1 (en) | Dye-sensitized solar cell using window film | |
| KR101091779B1 (en) | A method for manufacturing transparent conducting layer, transparent conducting layer manufactured by the same, and dye sensitized solar cell comprising the same | |
| JPS622471B2 (en) | ||
| KR20150041354A (en) | High conduction flexible transparent electrodes formation methods | |
| KR20150049922A (en) | Method of forming electrode for dye sensitive solar cell using surface pattering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |