200932958 八、發明說明： 【發明所屬之技術領域】 本創作為-種可提升染料敏化太陽能電池光電轉換效率的 方法’在室溫下_電泳法製備多層Ti〇2薄膜，完成之薄膜 具有高表面平整度，經燒結後可得良好結構緻密性，以作為毕 料敏化太陽㈣池之工作_，城裝完錢之^料敏化 太％ «b電池具有面光電轉換效率。 〇 【先前技術】 能源危機是近年來十分熱門的話題，化石燃料—煤炭、石 油與天然氣，合計纟全球現在使用能雜量的百分之八十五以 上，估世，石油薇藏量只可再開採四十年，天然氣可開採六 十年g厌可開採一百一十七年，而核能發電的燃料源自轴 礦丄預估尚可開採七十七年。可看純在全世界依賴最深的主 t源石献天然氣’在二十—世紀的前半，就將日趨枯竭。 隨者諸多產地薇藏量降低甚至枯竭，全球將面臨能源價格劇烈 波動，將衝擊全球經濟發展。 然而’過度的依賴石化能源只是;^口速能源的浩劫。此外， 均為汗染性能源，產生的％、C〇、％及氮氧化物 W嚴重城钟，近年來先進國家積極發展代綠色源來解決 未來將面_考驗，綠色能源因此被魏。綠色·中又以太 陽能為主流。 5 200932958 太陽能是一種取之不盡並且對環境無污染的綠色能源。每 年照射到地球表面的太陽能’估計為1.78x1017瓦-年，約為目 刖全世界母年所需能量的一萬多倍。太陽能電池多以結晶砂為 主流，占居80%的市場，但由於成本昂貴，在民間工業上的使 用上未能普及。直到新一代的太陽能電池_染料敏化太陽能電池 的出現。 習知之相關專利如染料敏化太陽能的模組設計、複合量子 © 點層之染料敏化太陽能電池、凝固態染料敏化太陽能電池、有 機染料的製備等，上述技術都著重於模組製造或是材料的改 質所化費的5免備成本與材料成本亦相當高，如金、銀的貴金 屬，對於染料敏化太陽能電池以低成本為出發點，明顯有所衝 突’且在薄膜的表面物理特性未有指出。 有鑑於此，本發明利用電泳分層技術製備光電極並運用於 染料敏化太陽能電池中，成功克服光電極表面裂縫情形，明顯 ❹ 料光電繼效率’職_設備成本與㈣成本，亦相對低 廉。 _ 【發明内容】 本創作主要於架設一電泳設備，利用電泳技術將刃〇2奈 米顆粒附著在導電基板(IT〇/FT〇/pET)上，利用電泳法沈積出 之薄膜經過燒結後具有高贿度的雜及難間的孔隙散布 均勻’得以讓染料分子以官能基鍵結在Ή〇2顆粒表面，而形成 電子傳輸時重要的關鍵。亦即由於奈米Ti〇2表面與染料分子是 6 200932958 以S能基麟之’在電解f為液體的情況下，未與奈米叫 表面鍵結之染料分子易受電解f的影響而脫^，脫落之染料^ 子無法將電子傳輸至半導體材料，影響電子傳遞。換句話說， 讓染料激發出的電子在第一時間直接與半導體材料進行電^的 ^輸’不至於有電子散失的現象，因而達到更高的效率。為了 提升染料敏化太陽能電池之效率，本發_容分為兩部分： 第-部分為電泳沈積法，請參考圖—之賴組成，包括銘片！， ❾ 奈米二氧化鈦顆粒2，電泳懸浮液（異丙醇）3，二氧化鈦薄膜 4，第-透明導電基板(IT0/FT0/PET) 5 ’電泳槽6及電源供應 器7，其中鋁片1作為電泳裝置之正電極。 第二部分為染料敏化太陽能電池的組裝如下，請參考圖二，主 要結構包含：第一透明導電基板(IT0/FT0/PET)8，光敏化染料 9，奈米二氧化鈦1〇，電解質層u，導體層12，第二透明導電 基板(ITO/FTO/PET) 13 ; I -V curve 量測儀 14。其中第一 ❹ 透明導電基板（IT0/FT0/PET)8與多孔隙二氧化鈦層 10組成正電極，而第二透明導電基板13與導體層12 組成反電極。 【實施方式】 本發明之實施方式分成二項說明 (1) Ti〇2薄膜的準備與特性：200932958 VIII. Description of the invention: [Technical field to which the invention belongs] This is a method for improving the photoelectric conversion efficiency of a dye-sensitized solar cell. A multilayer Ti〇2 film is prepared by electrophoresis at room temperature, and the film is high. The flatness of the surface, after sintering, can obtain good structural compactness, as the work of sensitizing the sun (four) pool _, the material sensitization of the city is too%% «b battery has surface photoelectric conversion efficiency. 〇[Prior Art] The energy crisis is a hot topic in recent years. Fossil fuels – coal, oil and natural gas – together with more than 85 percent of the world’s current energy use, are estimated to be limited. After 40 years of re-exploitation, natural gas can be mined for 60 years and can be mined for 117 years. The fuel for nuclear power generation is derived from the shaft mine. It is estimated that it can be mined for 77 years. It can be seen that pure natural gas, which relies on the deepest main source in the world, will be exhausted in the first half of the 20th century. With the loss of or even depletion of many places of origin, the world will face violent fluctuations in energy prices, which will impact the global economic development. However, 'excessive dependence on petrochemical energy is only a catastrophe; In addition, all of them are sweat-dyeing energy, and the %, C〇, % and NOx are serious city clocks. In recent years, advanced countries have actively developed generations of green sources to solve future challenges. Green energy has therefore been adopted by Wei. Green and medium-to-sun are the mainstream. 5 200932958 Solar energy is an inexhaustible and environmentally friendly green energy source. The amount of solar energy that hits the Earth's surface every year is estimated to be 1.78x1017 watt-years, about 10,000 times more than the energy needed to see the world's motherhood. Most of the solar cells use crystalline sand as the mainstream, occupying 80% of the market, but due to the high cost, the use in the private industry has not been popularized. Until the emergence of a new generation of solar cells _dye sensitized solar cells. Related patents such as dye sensitized solar module design, composite quantum dot layer dye-sensitized solar cells, solidified dye-sensitized solar cells, preparation of organic dyes, etc., all of which focus on module manufacturing or The cost of material modification and the cost of materials are also quite high. For example, precious metals such as gold and silver have obvious conflicts for the low cost of dye-sensitized solar cells, and the physical properties of the surface of the film. Not pointed out. In view of this, the present invention utilizes electrophoretic delamination technology to prepare photoelectrode and apply it to dye-sensitized solar cells, successfully overcoming the surface crack condition of the photoelectrode, and obviously illuminating the photo-electrical efficiency, and the cost of the device is relatively low. . _ 【Contents】 This creation is mainly to set up an electrophoresis device to attach the 2 nanometer particles of the blade to the conductive substrate (IT〇/FT〇/pET) by electrophoresis. The film deposited by electrophoresis has been sintered. The high brittleness of the heterogeneous and difficult pores spread evenly allows the dye molecules to bond with the functional groups on the surface of the Ή〇2 particles, forming an important key to electron transport. That is, since the surface of the titanium Ti〇2 and the dye molecule are 6 200932958, in the case where the electrolytic f is liquid, the dye molecules not bonded to the surface of the nano surface are susceptible to the electrolysis f. ^, the detached dye ^ can not transmit electrons to the semiconductor material, affecting electron transfer. In other words, the electrons excited by the dye are directly electrically connected to the semiconductor material at the first time without the phenomenon of electron loss, thereby achieving higher efficiency. In order to improve the efficiency of the dye-sensitized solar cell, the volume is divided into two parts: The first part is the electrophoretic deposition method, please refer to the figure - the composition, including the name film! , 奈 nano titanium dioxide particles 2, electrophoretic suspension (isopropanol) 3, titanium dioxide film 4, first transparent conductive substrate (IT0/FT0/PET) 5 'electrophoresis tank 6 and power supply 7, wherein aluminum sheet 1 The positive electrode of the electrophoresis device. The second part is the assembly of the dye-sensitized solar cell. Please refer to Figure 2, the main structure includes: the first transparent conductive substrate (IT0/FT0/PET) 8, the photosensitizing dye 9, the nano titanium dioxide 1〇, the electrolyte layer u , conductor layer 12, second transparent conductive substrate (ITO/FTO/PET) 13; I-V curve measuring instrument 14. The first transparent conductive substrate (IT0/FT0/PET) 8 and the porous titanium dioxide layer 10 constitute a positive electrode, and the second transparent conductive substrate 13 and the conductive layer 12 constitute a counter electrode. [Embodiment] The embodiment of the present invention is divided into two parts. (1) Preparation and characteristics of Ti〇2 film:
使用的基板(substrate)為FTO(fluorine-doped tin oxide)、ITO 7 200932958 (出出1皿仳〇说6)與？丑丁(?〇1丫她咖11你哪11如），由於打〇為可 耐熱至55(TC ’但ITO透光率較優且價錢較1?丁〇便宜，但只可承 受到400 C，此外，以PET為基底僅能承受g〇〇c。故在燒結溫度 的控制需配合所選擇的基底。運用電泳法製備多層薄膜在 ITO/FTO/PETJi，電泳法细帶電粒子往相反的電極移動達到 沉積的目的，當奈米顆粒在電泳懸浮液中呈現旋浮穩定時， 因顆粒表面帶電，藉此以相反電荷吸引顆粒使奈米顆粒沉積於 Ο 一基板上。本發明重點在於薄膜厚度、緻密度、表面平整度對 於光電轉換效率的影響。設定電源供應器之電壓為 40V(〜21mA/Cm2)，並控制整體沈積厚度為1〇雖，且以分層術 改善薄膜裂縫，再經過燒結處理以改善薄膜緻密性，以完成染 料敏化太陽能電池光電極的製備。如圖三所示為單層薄膜之 SEM圖，圖中顯示薄膜表面有明顯裂縫。圖四為以電泳堆疊的 方式完成所需之厚度的多層薄膜斷面SEM圖，且控制每層厚度 ❹約3.3圖五為分層電泳後再經過燒燒結處理後之多層薄膜 SEM圖，圖中顯示薄膜表面裂縫已有明顯的改善。 (2)染料敏化太陽能電池的組裝： 光電極與染料分子進行官能基鍵結，染料選擇以貴金屬元 素錯合物（N-719、N_3、Black dye)或天然染料。而反電極(導 體層12與第二導電基板組合者⑼以碳黑和石墨以比例1〇:9〇混 合，再以刮刀塗佈法、磁控濺射法沈積於FTO完成。將完成之 各層結構進行封裝，之後注射電解韻，而完成的染料敏化太 8 200932958 陽能電池組合結構’並量測其光電性質。當光照射進入光電極 中，染料敏化太陽能電池開始作動產生電能，其發電機制如下· 1·太陽光照入射使得吸附在取1〇的染料分子(D)9，從原本 的激態要升至激發態(D*)。 D + hv —> D* 2.激發態的染料分子(1>)丟出電子傳入Ti〇2的傳導帶中， 而產生氧化鈦的染料分子(D+)。 〇 —> D+ + e' 1電子傳人Τι〇2 10傳導帶中導電基板g經由外部電路傳 入輔助導體層12。電子在輔助導體層12表面與電解質νΐι進 行還原反應成Γ。The substrate used is FTO (fluorine-doped tin oxide), ITO 7 200932958 (out of 1 dish 仳〇 said 6) and ? Ugly Ding (? 〇 1 丫 her coffee 11 you 11), because the snoring is heat resistant to 55 (TC 'but ITO light transmittance is better and the price is cheaper than 1? Ding, but can only withstand 400 C In addition, the PET substrate can only withstand g〇〇c. Therefore, the control of the sintering temperature needs to match the selected substrate. The multilayer film is prepared by electrophoresis in ITO/FTO/PETJi, and the charged particles are electrophoresis to the opposite electrode. The movement reaches the purpose of deposition. When the nanoparticle exhibits a cyclonic stability in the electrophoretic suspension, the surface of the particle is charged, thereby attracting the particles with opposite charges to deposit the nanoparticle on the substrate. The present invention focuses on the film thickness. , density, surface flatness effect on photoelectric conversion efficiency. Set the voltage of the power supply to 40V (~21mA/Cm2), and control the overall deposition thickness to 1〇, and improve the film cracks by delamination. Sintering treatment to improve the compactness of the film to complete the preparation of the photoelectrode of the dye-sensitized solar cell. As shown in Fig. 3, the SEM image of the single-layer film shows obvious cracks on the surface of the film. Complete the SEM image of the multilayer film with the required thickness, and control the thickness of each layer to be about 3.3. Figure 5 is the SEM image of the multilayer film after layered electrophoresis and then sintered. The film shows that the surface crack of the film has been obvious. Improvement (2) Assembly of dye-sensitized solar cells: The photoelectrode is functionally bonded to the dye molecules, and the dye is selected as a noble metal element complex (N-719, N_3, Black dye) or a natural dye. The conductor layer 12 and the second conductive substrate combiner (9) are mixed with carbon black and graphite in a ratio of 1 〇:9 ,, and then deposited by the doctor blade coating method and magnetron sputtering method on the FTO. The completed layers are packaged. After the injection of electrolysis rhyme, and completed dye sensitization 8 200932958 cation battery combination structure 'and its photoelectric properties. When the light is irradiated into the photoelectrode, the dye-sensitized solar cell starts to generate electricity, the generator system is as follows · 1. The incidence of sunlight is such that the dye molecule (D) 9 adsorbed on the 1 , is raised from the original excited state to the excited state (D*). D + hv —> D* 2. The excited state of the dye molecule ( 1>) throwing out electronic transmission Into the conduction band of Ti〇2, a dye molecule (D+) of titanium oxide is produced. 〇-> D+ + e' 1 electron transfer Τι〇2 The conductive substrate g in the conduction band is transmitted to the auxiliary conductor layer 12 via an external circuit. The electrons are reduced in reaction with the electrolyte νΐ on the surface of the auxiliary conductor layer 12 to form ruthenium.
Is' + 2e' —> 3Γ 4.氧化態的染料(D+)與1_進行還原反應，回到基態。 2D+ + 2Γ —> 2D + 12 5·而Γ與12則會再度成為電解質13·。 如此完成一次循環，電流因此產生，因而產生電能。效率的 量測以I-V curve量測儀14作為光電轉換效率檢測之設備。圖 六所示為不同層數薄膜之染料敏化太陽能電池之n curve圖，圖中顯示單層薄膜其效率值僅為i 03%，三層薄 膜則可大為提升至5.29%。 9 200932958 【圖式簡單說明】 圖一本發明之電泳設備示意圖 圖=本發明之賴敏化太雜電池之結構示意圖。 圖三單層薄膜表面裂縫的SEM圖 圖四利用電泳分層技術的薄膜剖面SEM圖 圖五多層薄膜表面裂縫改善的SEM圖 圖不同層數之薄膜染料敏化太陽能電池之i-v curve 圖 【主要元件符號說明】 圖―《 . 1鋁片 2奈米一氧化欽顆粒 3電泳懸浮液（異丙醇） 4二氧化鈦薄膜 5第一透明導電基板（氧化銦錫或氧化 氟錫及導電聚合物（IT0/FT0/PET)) 6電泳槽 7電源供應器 圈二· 8第一透明導電基板（氧化銦錫或氧化 氟錫及導電聚合物（IT0/FT0/PET)) 9光敏化染料 10奈米二氧化欽 11電解質層 12導體層 10 200932958 13第二透明導電基板（氧化銦錫或氧化 氟錫及導電聚合物（IT0/FT0/PET)) 14 I-V curve 量測儀 卜、申請專利範圍：Is' + 2e' —> 3Γ 4. The dye (D+) in the oxidation state undergoes a reduction reaction with 1_ and returns to the ground state. 2D+ + 2Γ —> 2D + 12 5· and Γ and 12 will again become electrolyte 13·. By doing this once, the current is generated, thus generating electrical energy. The measurement of the efficiency is performed by the I-V curve measuring instrument 14 as a device for photoelectric conversion efficiency detection. Figure 6 shows the n-curve of a dye-sensitized solar cell with different layers of film. The figure shows that the single-layer film has an efficiency of only i 03%, and the three-layer film can be greatly improved to 5.29%. 9 200932958 [Simplified description of the drawings] Fig. 1 is a schematic view of the electrophoresis apparatus of the present invention. Fig. is a schematic view showing the structure of the sensitized and sterilized battery of the present invention. Fig.3 SEM image of surface cracks of single-layer filmFig.4 SEM image of film profile using electrophoretic layering technologyFig.5 SEM image of surface crack improvement of multi-layer film. iv curve diagram of film dye-sensitized solar cells with different layers Component symbol description] Figure - "1 aluminum sheet 2 nano-oxidized granules 3 electrophoresis suspension (isopropanol) 4 titanium dioxide film 5 first transparent conductive substrate (indium tin oxide or oxyfluoride oxide and conductive polymer (IT0) /FT0/PET)) 6 Electrophoresis tank 7 power supply ring 2.8 first transparent conductive substrate (indium tin oxide or oxyfluoride oxide and conductive polymer (IT0/FT0/PET)) 9 photosensitizing dye 10 nm II Oxidation 11 electrolyte layer 12 conductor layer 10 200932958 13 second transparent conductive substrate (indium tin oxide or oxyfluoride oxide and conductive polymer (IT0/FT0/PET)) 14 IV curve measuring instrument, patent application scope:
• (a) —種電泳沉積薄膜設備：包含：鋁片，奈米二氧 化欽顆’電泳懸浮液（異丙醇），二^化鈦薄 膜’第一透明導電基板（IT0/FT0/PET)，電泳 槽，電源供應器。 < 2· (b)—種染料敏化太陽能電池裝置，其主要包含： 一第一透明導電基板（IT0/FT0/PET)，其與一多 孔隙二氧化鈦層形成於正電極；一光敏染料声， ，於正電極中之孔隙間；一第二透明導電基&， /、與一導體層形成於反電極；一電解質層， 於第一透明導電基板與第二透明導電基板之間。• (a) Electrophoretic deposition film equipment: Contains: aluminum sheet, nano-dioxide crystal electrophoresis suspension (isopropyl alcohol), titanium dioxide film 'first transparent conductive substrate (IT0/FT0/PET) , electrophoresis tank, power supply. < 2· (b) A dye-sensitized solar cell device, comprising: a first transparent conductive substrate (IT0/FT0/PET) formed on a positive electrode with a porous titanium dioxide layer; , between the pores in the positive electrode; a second transparent conductive group &, / and a conductor layer formed on the counter electrode; an electrolyte layer between the first transparent conductive substrate and the second transparent conductive substrate.
如申請專利範圍第1項（a)之所述，電泳懸浮液中載液 為異丙醇（IPA)。 .2申凊專利範圍第1項（a)之所述，電泳裝置正電極為銘 溥片。 4.=請專利範圍第i項⑹之所述，染料敏化太陽能 電池中，其中該第一透明導 攻月導電基板與第二透明導 Z板係為氧化銦錫或氧化氟錫(IT0/FT0)導電 底在可繞性聚合物上的導電基 11The carrier liquid in the electrophoretic suspension is isopropanol (IPA) as described in item 1 (a) of the patent application. .2 As stated in item 1 (a) of the patent scope, the positive electrode of the electrophoresis device is an inscription. 4. In the dye-sensitized solar cell, wherein the first transparent guiding moon-conducting substrate and the second transparent conducting Z-plate are indium tin oxide or oxyfluoride oxide (IT0/). FT0) Conductive base on the conductive polymer on the flexible polymer 11