201216493 六、發明說明： c發明所屬·^技斗标領域3 發明領域 本發明係關於一種染料敏化太陽能電池，詳言之係有 關一種可隔絕由於内部電池單元之功能降低，而造成模組 功能降低之影響之染料敏化太陽能電池，及其製造方法。 L先前时;j 發明背景 於1991年度，瑞士國立洛桑聯邦理工學r(epFL)邁克 爾•格蘭澤爾（Michael Gratzel)研究團隊開發出染料敏化奈 米粒子氧化鈦太陽能電池以後，在該領域已推進許多研究。 相較於既有的矽基系太陽能電池，染料敏化太陽能電 池之製造成本低，因此期待可取代既有的非晶矽太陽能電 池。不同於石夕基太陽能電池，染料敏化太陽能電池係光電一 化學性太陽能電池，其主要構成材料包括：純分子，係 吸收可見光’生成電子_電洞(_)對者；及過渡金屬氧化 物’係傳遞已生成之電子者。 -般的染料敏化太陽能電池之電池單元構造係以前面 透明基板、後面透明基板及導電性透明電極作為基本構成 要素^述導電性透明電極形成於前面/後面透明基板之 各表面。料面剌基板之導雜㈣電極，形成有過渡 金屬氧化物之例如Ti〇2多孔質層。於奈米粒子多孔質⑽ 之表面吸附有染料。於後面透明基板之導電性透明電極， t成有觸媒電極。賊，於加2多孔質層與觸媒電極之間 3 201216493 填充電解質。 木料敏化太陽能電池產生電的原理係當染料吸收到光 時s激發染料内部之電子，移動至聊多孔質層並到達 外部電極，-r jj/ ,, 攸而形成一極，染料之電子脫離處係藉由存在 於電解質巾之雜子之氧化作用，㈣電子進行移動而予 以真埋°峨料餘㈣電極#丨移動，於觸媒電極表面， 从 原作用而再度接受電子供給。此時，電壓係由Ti02 之傳導f最下層之能量位準、與觸媒電極表面之碘離子之 還原位準的差距來決定。 然而’染料敏化太陽能電池在面積小至lcm2以下時， 率效率仍向，但若製造成大面積，則功率效率會由於 基板與材料之電阻而急遽下降。因此，為了製造成大面積 模組而將鄰接電池單元予以電連結。第1圖係本發明申請人 所申清的染料敏化太陽能電池模組，其具有後面基板貫穿 之連結電極(韓國專利申請案第1〇 2〇1〇 5〇〇96號）。 如第1圖所示，具有貫穿後面基板之連結電極之染料敏 化太陽能電池模組包含：前面透明基板111與後面透明基板 121 ;前面導電層131、141與後面導電層133、143 ; Ti〇2多 孔質層132、142與觸媒電極134、144;電解質層136、146 ; 及作為絕緣層之密封部135a、135b、145a、145b ;然後尚 包含連結電極15卜152,係電連結第1電池單元之前面導電 層131與第2電池單元之後面導電層143者。連結電極151、 152係於後面透明基板121開出通孔，通過該通孔而插入。 進而言之，於前面導電層131及後面導電層143，形成 4 201216493 有集電電極（未圖示），連結電極161連結前面導電層131之集 電電極與後面導電層143之集電電極。以下為了便於圖示及 說明，說明連結電極151連結第1電池單元之前面導電層131 與第2電池單元之後面導電層143。 該類構造之染料敏化太陽能電池雖然連結電極之寬度 窄，但電連結良好，提高模組整體之發電效率。 然而，由於該類染料敏化太陽能電池亦是連結許多電 池單元的構造，因此在一部分電池單元未發揮其功能時， 整體模組之發電效率有時會降低。 【發明内容】 發明概要 發明欲解決之課題 本發明係用以解決在染料敏化太陽能電池模組有發生 之虞之發電效率降低問題，其目的在於即便由於内部或外 部要因，預定電池單元或許多電池單元未發揮其功能，仍 使得其他電池單元所生成電力之引出完全不受影響，並使 得模組整體之發電效率不降低。 用以欲解決課題之手段 為了達成該類目的，本發明之染料敏化太陽能電池在 構成上包含：前面基板及後面基板，係形成有構成許多電 池單元之圖案導電層者；第1前面集電電極，係形成於第1 電池單元之前面基板上者；第2後面集電電極，係形成於與 第1電池單元相鄰接之第2電池單元之後面基板上者；密封 部，係形成於第1電池單元與第2電池單元之間，於内部形 5 201216493 成連結第1前面集電電極與第2後面集電電極之空間者；第1 連結電極，係於位置對應於密封部之空間之後面基板，具 備通孔，插入於通孔而電連結第1前面集電電極與第2後面 集電電極者；第2連結電極，係與第1連結電極相鄰接者； 第1及第2引線，係分別電連結於第1及第2連結電極者；及 單向導通元件，係一端連結於前述第1引線，另一端連結於 前述第2引線者。 單向導通元件得為單向二極體。 第1及第2引線與第1及第2連結電極之電連接可利用如 下方式：以焊錫等焊接之方式；或利用微小螺栓，於螺栓 捲繞引線後，將此旋緊結合於連結電極之方法等。該類方 法宜於連結電極某程度硬化後才使用。此外，若於連結電 極插入於通孔時，將引線一同插入，則於連結電極硬化的 同時，引線亦固定於連結電極，該方式亦可使用。 第1及第2連結電極係插入於通孔之内部，此時，通孔 之一部分殘留為空的空間，該空間宜由填充材料所填滿。 第1及第2連結電極可充滿於通孔，此時，不需要填充 材料。 本發明之染料敏化太陽能電池之製造方法包含以下階 段：於前面基板，形成構成電池單元之導電層圖案、多孔 質層、前面集電電極之階段；於後面基板，形成構成電池 單元之導電層圖案、電解液注入孔及連結電極通孔、觸媒 電極、後面集電電極之階段；在將相鄰接之電池單元予以 絕緣之密封部之内部形成空間地介有熱塑性物質後，黏合 6 201216493 月|J面基板與後面基板之階段，通過前面基板之通孔而注入 連結電極之階段；於連結電極連結引線之階段；於引線連 結單向導通元件之階段；及通過後面基板之電解液注入孔 而注入電解液之階段。 於引線連結階段後’若通孔之一部分殘留為空的空 間’則可進一步經過以填充材料填充該空間之階段。 單向導通元件得為單向二極體。 本發明之染料敏化太陽能電池之其他製造方法可由以 下階段構成：於前面基板，形成構成電池單元之導電層圖 案、多孔質層、前面集電電極之階段；於後面基板，形成 構成電池單元之導電層圖案、電解液注入孔及連結電極通 孔、觸媒電極、後面集電電極之階段；在將相鄰接之電池 單元予以絕緣之密封部之内部形成空間地介有熱塑性物質 後’黏合前面基板與後面基板之階段；封閉後面基板之通 孔之階段；通過後面基板之電解液注入孔而注入電解液之 階段；封住電解液注入孔之階段；開放後面基板之通孔之 階段；通過後面基板之通孔而注入連結電極之階段；於連 結電極連結引線之階段；及於引線連結單向導通元件之階 段。 於該方法，於引線連結階段後，若通孔之一部分殘留 為空的空間，則宜進一步包含以填充材料填充該空間之階 段。 發明效果 如此，具有單向二極體之染料敏化太陽能電池模組係 201216493 即便由於内部或外部要因，預定電池單元或許多電池單元 未發揮其功能，仍不會對其他電池單元所生成電力造成影 響，模組整體之發電效率不會降低。 圖式簡單說明 第1圖係具有後面基板貫穿之連結電極之染料敏化太 陽能電池模組之剖面圖。 第2a圖係本發明之單向二極體與第1形態之連結電極 相連結之染料敏化太陽能電池模組之剖面圖。 第2b圖係本發明之單向二極體與第2形態之連結電極 相連結之染料敏化太陽能電池模組之剖面圖。 第3a圖係說明製造前面基板之過程之圖式。 第3b圖係說明製造後面基板之過程之圖式 第3c圖係說明黏合前面基板與後面基板而完成本發明 之染料敏化太陽能電池之過程之圖式。 第4 a及4 b圖係於由4個電池單元所構成的2個染料敏化 太陽能電池模組，其一對1個電池單元附著單向二極體，另 一維持不附著單向二極體，一面遮蔽1個電池單元之光電極 面一面測定時所示之電流-電壓曲線。 I：實施方式3 用以實施發明之形態 以下參考附圖來詳細說明本發明。 第2 a圖係本發明之單向二極體與第1形態之連結電極 相連結之染料敏化太陽能電池模組之剖面圖。 如第2a圖所示，第1實施例包含：前面透明基板111與 8 201216493 後面透明基板121 ;前面導電層131、141與後面導電層133、 143 ; Ti02多孔質層132、142與觸媒電極134、144 ;電解質 層136、146 ;及作為絕緣層之密封部135a、135b、145a、 145b ;然後尚包含：連結電極151、152，係電連結第1電池 單元之前面導電層131與第2電池單元之後面導電層143 者；焊接部311 ;引線3之1、322 ;及單向二極體331等。 前面透明基板111與後面透明基板121係由包含PET、 PEN、PC、PP、PI、TAC中之某—者之透光性塑膠基板或 玻璃基板所構成。 前面導電層131、141或後面導電層133、143可構成為’ 被覆膜於前面透明基板111或後面透明基板〗2i表面之形 態。前面導電層131、141或後面導電層133、143可由ITO、 FTO、ZnO-(Ga2〇3 或 Al2〇3)、Sn0rSb203 中之某一者所構成。 Τι〇2多孔質層132、142得為厚度1〜4〇μιη之多孔質膜。 構成多孔質膜之奈米粒子之平均粒徑宜為3〜1〇〇nm程度， 進而宜具有10〜40mn之粒徑。若從構成多孔質膜之代表性 物負丁1〇2之粒杈類別之功率效率來看，Ti〇2之粒徑小於 10nm時，在成膜後熱處理時，密合度可能降低而引起剝離。 反之，Τι〇2之粒徑大於4〇11111時，表面積變小，染料吸附點 減少，其結果，光電轉換效率有時會降低。因此，當全面 考慮製程及功率效率時，宜利用粒徑1〇〜4〇nm2Ti〇2。 就多孔質層而言，重要之處在於奈米粒子均勻分布， 或維持多孔性而同時表面具有適度的粗度。表面粗度宜大 於 20nm。 201216493 於多孔性膜，為了讓電子容易移動，可添加諸如摻雜 錫之氧化銦(ITO : tin-doped indium oxide)之導電性微粒。 又，為了延長光路’亦可添加光散射子。 於第1實施例，利用Ti氧化物作為多孔質層，但Nb氧化 物、Zn氧化物、Sn氧化物、Ta氧化物、W氧化物、Ni氧化 物、Fe氧化物、Cr氧化物、V氧化物、Pm氧化物、Zr氧化 物、Sr氧化物、In氧化物、Yr氧化物、La氧化物、Mo氧化 物、Mg氧化物、A1氧化物、Y氧化物、Sc氧化物、Sm氧化 物、Ga氧化物、In氧化物、SrTi氧化物等亦可單獨利用， 或利用於複合物的形態。 於多孔質層之奈米粒子表面，若為用於染料敏化太陽 能電池之染料均可，並未特別限定，宜以釕(Ru)系染料為 佳。Ru係屬於鉑族之元素，可製作許多有機金屬複合化合 物。作為具體一例，適於染料敏化太陽能電池之染料包括201216493 VI. Description of the invention: c invention belongs to the field of technology 3 FIELD OF THE INVENTION The present invention relates to a dye-sensitized solar cell, in particular to a module that can be isolated due to a reduced function of the internal battery unit A dye-sensitized solar cell having a reduced effect, and a method of manufacturing the same. L Previous Time; j Background of the Invention In 1991, the Swiss National Institute of Science and Technology of Lausanne (epFL) Michael Gratzel research team developed dye-sensitized nanoparticle titanium oxide solar cells in the field Many studies have been advanced. Dye-sensitized solar cells are low in manufacturing cost compared to existing germanium-based solar cells, and are therefore expected to replace existing amorphous germanium solar cells. Different from Shi Xiji solar cells, dye-sensitized solar cells are photoelectric-chemical solar cells, whose main constituent materials include: pure molecules, which absorb visible light 'to generate electrons_holes' (_) pairs; and transition metal oxides 'The system passes the generated electrons. In the battery cell structure of the dye-sensitized solar cell, the front transparent substrate, the rear transparent substrate, and the conductive transparent electrode are used as basic constituent elements, and the conductive transparent electrodes are formed on the respective surfaces of the front/back transparent substrate. The impurity-conducting (four) electrode of the substrate , substrate is formed with a porous metal oxide such as a Ti〇2 porous layer. A dye is adsorbed on the surface of the nanoparticle porous (10). The conductive transparent electrode of the transparent substrate is t-shaped with a catalyst electrode. Thief, between the 2 porous layer and the catalytic electrode 3 201216493 filled with electrolyte. The principle of electricity generated by wood-sensitized solar cells is that when the dye absorbs light, it stimulates the electrons inside the dye, moves to the porous layer and reaches the external electrode, -r jj/ , , and forms a pole, and the electrons of the dye are separated. The process is carried out by the oxidation of the miscellaneous ions present in the electrolyte towel, and (4) the electrons are moved to be buried, and the remaining (four) electrodes are moved, and the electron supply is again received from the original action on the surface of the catalyst electrode. At this time, the voltage is determined by the difference between the energy level of the lowermost layer of the conduction f of Ti02 and the reduction level of the iodide ion on the surface of the catalyst electrode. However, when the area of the dye-sensitized solar cell is as small as 1 cm or less, the rate efficiency is still good, but if it is made into a large area, the power efficiency is drastically lowered due to the resistance of the substrate and the material. Therefore, adjacent battery cells are electrically connected in order to manufacture a large-area module. Fig. 1 is a dye-sensitized solar cell module as claimed by the applicant of the present invention, which has a connecting electrode through which a rear substrate is inserted (Korean Patent Application No. 1〇2〇1〇5〇〇96). As shown in FIG. 1, the dye-sensitized solar cell module having the connecting electrode penetrating the rear substrate comprises: a front transparent substrate 111 and a rear transparent substrate 121; front conductive layers 131, 141 and rear conductive layers 133, 143; 2 porous layers 132 and 142 and catalyst electrodes 134 and 144; electrolyte layers 136 and 146; and sealing portions 135a, 135b, 145a, and 145b as insulating layers; and then connecting electrodes 15 and 152, and electrically connecting the first The battery unit front surface conductive layer 131 and the second battery unit rear surface conductive layer 143. The connection electrodes 151 and 152 are connected to the transparent substrate 121 at the rear to open a through hole, and are inserted through the through hole. Further, in the front conductive layer 131 and the rear conductive layer 143, 4 201216493 is formed with a collector electrode (not shown), and the connection electrode 161 connects the collector electrode of the front conductive layer 131 and the collector electrode of the rear conductive layer 143. Hereinafter, for convenience of illustration and description, the connection electrode 151 is connected to the front surface conductive layer 131 of the first battery unit and the second surface unit rear surface conductive layer 143. The dye-sensitized solar cell of this type has a narrow connection width, but has good electrical connection and improves the overall power generation efficiency of the module. However, since such a dye-sensitized solar cell is also a structure in which a large number of battery cells are connected, when a part of the battery cells do not function, the power generation efficiency of the entire module may be lowered. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention is to solve the problem of power generation efficiency reduction after occurrence of a dye-sensitized solar cell module, and the object thereof is to reserve a battery cell or many even if it is due to internal or external factors. The battery unit does not function, and the power generated by the other battery units is completely unaffected, and the power generation efficiency of the module as a whole is not lowered. Means for Solving the Problem In order to achieve the above object, the dye-sensitized solar cell of the present invention comprises: a front substrate and a rear substrate, which are formed with patterned conductive layers constituting a plurality of battery cells; The electrode is formed on the front substrate of the first battery unit; the second rear collector electrode is formed on the rear substrate of the second battery unit adjacent to the first battery unit; and the sealing portion is formed on the substrate Between the first battery unit and the second battery unit, the first front collecting electrode and the second rear collecting electrode are connected to each other in the internal shape 5 201216493; the first connecting electrode is in a space corresponding to the sealing portion. The surface substrate is provided with a through hole, and is inserted into the through hole to electrically connect the first front collecting electrode and the second rear collecting electrode; the second connecting electrode is adjacent to the first connecting electrode; The two leads are electrically connected to the first and second connection electrodes, respectively, and the one-way conduction element is one end connected to the first lead and the other end connected to the second lead. The unidirectional conduction element is a unidirectional diode. The electrical connection between the first and second leads and the first and second connecting electrodes can be performed by soldering or the like; or by using a minute bolt, after the lead is wound by the bolt, the screw is coupled to the connecting electrode. Method, etc. This method is suitable for use after the connecting electrode has been hardened to some extent. Further, when the connecting electrode is inserted into the through hole, the lead wire is inserted together, and the lead wire is also fixed to the connecting electrode while the connecting electrode is hardened. This method can also be used. The first and second connection electrodes are inserted into the inside of the through hole. At this time, a part of the through hole remains as an empty space, and the space is preferably filled with a filling material. The first and second connection electrodes may be filled in the through holes, and at this time, no filling material is required. The method for manufacturing a dye-sensitized solar cell of the present invention comprises the steps of: forming a conductive layer pattern constituting a battery cell, a porous layer, and a front collector electrode on a front substrate; and forming a conductive layer constituting the battery cell on the rear substrate a pattern, an electrolyte injection hole, and a stage of connecting the electrode through hole, the catalyst electrode, and the rear collector electrode; forming a space inside the sealing portion that insulates the adjacent battery unit to form a thermoplastic material, and bonding 6 201216493 Month|the stage of the J-side substrate and the rear substrate, the stage of injecting the connection electrode through the through hole of the front substrate; the stage of connecting the connection line of the electrode; the stage of connecting the wire to the one-way conduction element; and the injection of the electrolyte through the rear substrate The stage of injecting the electrolyte into the hole. After the wire bonding stage, if the space of one of the through holes remains empty, the stage of filling the space with the filling material can be further passed. The unidirectional conduction element is a unidirectional diode. The other manufacturing method of the dye-sensitized solar cell of the present invention may be constituted by forming a conductive layer pattern constituting the battery cell, a porous layer, and a front collecting electrode on the front substrate, and forming a battery unit on the rear substrate. a conductive layer pattern, an electrolyte injection hole, and a stage of connecting the electrode through hole, the catalyst electrode, and the rear collector electrode; forming a space inside the sealing portion that insulates the adjacent battery unit, and then forming a space a stage of the front substrate and the rear substrate; a stage of closing the through hole of the rear substrate; a stage of injecting the electrolyte through the electrolyte injection hole of the rear substrate; a stage of sealing the electrolyte injection hole; and a stage of opening the through hole of the rear substrate; The stage of injecting the connection electrode through the through hole of the rear substrate; the stage of connecting the connection line of the electrode; and the stage of connecting the wire to the one-way conduction element. In this method, after a wire bonding stage, if one of the through holes remains as an empty space, it is preferable to further include a stage of filling the space with a filling material. According to the invention, the dye-sensitized solar cell module having the one-way diode is 201216493. Even if the predetermined battery unit or a plurality of battery cells do not function due to internal or external factors, the power generated by the other battery cells is not generated. As a result, the overall power generation efficiency of the module will not decrease. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a dye-sensitized solar cell module having a connection electrode through which a rear substrate is inserted. Fig. 2a is a cross-sectional view showing a dye-sensitized solar cell module in which the unidirectional diode of the present invention is connected to the connection electrode of the first embodiment. Fig. 2b is a cross-sectional view showing a dye-sensitized solar cell module in which the unidirectional diode of the present invention is connected to the connection electrode of the second embodiment. Figure 3a is a diagram illustrating the process of fabricating the front substrate. Fig. 3b is a view showing a process of manufacturing a rear substrate. Fig. 3c is a view showing a process of bonding the front substrate and the rear substrate to complete the process of the dye-sensitized solar cell of the present invention. The 4th and 4th drawings are based on two dye-sensitized solar cell modules composed of four battery cells, one pair of one battery unit is attached to the one-way diode, and the other is maintained without attaching the one-way diode. The current-voltage curve shown when measuring the photoelectrode surface of one battery cell. I: Embodiment 3 Mode for Carrying Out the Invention Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Fig. 2a is a cross-sectional view showing a dye-sensitized solar cell module in which the unidirectional diode of the present invention is connected to the connection electrode of the first embodiment. As shown in FIG. 2a, the first embodiment includes: front transparent substrate 111 and 8 201216493 rear transparent substrate 121; front conductive layers 131, 141 and rear conductive layers 133, 143; Ti02 porous layers 132, 142 and catalytic electrodes. 134, 144; electrolyte layers 136, 146; and sealing portions 135a, 135b, 145a, 145b as insulating layers; then further comprising: connecting electrodes 151, 152, electrically connecting the first battery unit front surface conductive layer 131 and second The rear surface of the battery unit 143; the soldering portion 311; the lead 3 1, 322; and the unidirectional diode 331 and the like. The front transparent substrate 111 and the rear transparent substrate 121 are made of a translucent plastic substrate or a glass substrate including any one of PET, PEN, PC, PP, PI, and TAC. The front conductive layers 131, 141 or the rear conductive layers 133, 143 may be formed in the form of a coating film on the front transparent substrate 111 or the rear transparent substrate 2i surface. The front conductive layers 131, 141 or the rear conductive layers 133, 143 may be composed of one of ITO, FTO, ZnO-(Ga2〇3 or Al2〇3), and Sn0rSb203. The porous layer 132, 142 of the Τι〇2 is a porous film having a thickness of 1 to 4 μm. The average particle diameter of the nanoparticles constituting the porous film is preferably about 3 to 1 〇〇 nm, and more preferably has a particle diameter of 10 to 40 mn. When the particle size of Ti〇2 is less than 10 nm from the viewpoint of the power efficiency of the type of the crucible of the representative film constituting the porous film, the adhesion may be lowered during the post-film heat treatment to cause peeling. On the other hand, when the particle size of Τι〇2 is larger than 4〇11111, the surface area becomes small, and the dye adsorption point decreases, and as a result, the photoelectric conversion efficiency sometimes decreases. Therefore, when considering the process and power efficiency in a comprehensive manner, it is preferable to use a particle size of 1 〇 4 〇 nm 2 Ti 〇 2 . In the case of a porous layer, it is important that the nanoparticles are uniformly distributed, or that the porosity is maintained while the surface has a moderate thickness. The surface roughness should be greater than 20 nm. 201216493 In the porous film, in order to make electrons move easily, conductive particles such as tin-doped indium oxide (ITO) may be added. Further, a light scatterer may be added in order to extend the optical path. In the first embodiment, Ti oxide is used as the porous layer, but Nb oxide, Zn oxide, Sn oxide, Ta oxide, W oxide, Ni oxide, Fe oxide, Cr oxide, V oxidation , Pm oxide, Zr oxide, Sr oxide, In oxide, Yr oxide, La oxide, Mo oxide, Mg oxide, A1 oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, or the like may be used alone or in the form of a composite. The surface of the nanoparticle on the porous layer is not particularly limited as long as it is a dye for a dye-sensitized solar cell, and a Ru(R) dye is preferred. Ru is an element of the platinum group and can be used to make a plurality of organometallic composite compounds. As a specific example, a dye suitable for a dye-sensitized solar cell includes
Ru(etc bpy)2(NCS)22CH3CN類型。在此，etc係(COOEt)2或 (COOH)2，可與多孔質膜(Ti〇2)之表面結合之反應基。 觸媒電極134、144宜由鉑、碳、碳奈米管等所構成， 具有1〜300程度之厚度，光穿透率為ι〇〜100%。尤其始係 反射度良好而廣為使用。 電解質層136、146可選擇性地利用液體電解質、離子 性電解質、準固體電解質、高分子電解質、固體電解質等。 電解質係於前面透明基板111與後面透明基板121之間，均 勻分散於Ti〇2多孔質層136、146之内部。電解質為 idiode/tridiode層，發揮藉由氧化/還原而從觸媒電極134、 10 201216493 144接收電子，並傳遞至染料之作用。 作為絕緣層之密封部135a、135b、145a、145b有時係 已去除河面導電層13b 141或後面導電層133、143之一側 之溝槽，但本發明之密封部135a、135b、145a、145b係為 了形成後述之連結電極151、152所插入的空間，故宜構成 為一體成型。又，各密封部135a、135b、145a、145b係形 成為在前面導電層13卜141或後面導電層133、143已去除 後’一側端部延長至前面透明基板111或後面透明基板 121。於第2圖’例如若觀察1個密封部145a，密封部145a之 -側端部係if過前面導電層131、141已錯之_側部分， 並延長至前面透明基板111，密封部145a之另一側端部係延 長至後面導電層14 3之—側上部面而構成，但不限定於該類 形態’右可藉由相鄰接之密封部而於内部形成封閉空間， 則將密封部構成為任何形態均無妨。 將相鄰接之電池單元予以絕緣之密封部135b、145a所 I成的空間’係構成為與形成在透明基板i2i之通孔⑹、 162之位置一致。 連結電極151係電連結第1電池單元之前面導電層 131、與相鄰接之第2電池單元之後面導電層143。如前述， 實際上’連結電極151係電連結前面集電電極與後面集電電 極’而則述前面集電電極連結於第1電池單元之前面導電層 131 ’前述後面集電電極連結於第2電池單元之後面導電層 143 〇 連結電極151、152係經由形成在後面透明基板121之許 11 201216493 多通孔161、162而插入於密封部135b、145a之内部空間。 於第1實施例，當經由通孔161，以注射器注入熱硬化性之 導電性金屬之例如糊狀物(paste)或墨水(ink)形態之銀(Ag) 專，銀糊或銀墨水填滿於密封部135b、145a之内部空間時， 以烤箱在120〜17(TC程度之溫度下，予以熱硬化1〇〜3〇分 鐘，形成連結電極151。在此，銀糊或銀墨水係沿著通孔 161、162注入。於第h圖，連結電極151 ' 152係於已注入 的狀態下硬化，因此後面透明基板121之通孔16卜162係由 連結電極151、152所填滿。 於位在通孔161、162之後面透明基板方向之連結電極 151、152之端部’電結合引線321、322。在此，電結合之 方式可利用焊接等各種方式。 引線321、322係往後面透明基板121之方向引出，各引 線321、322係連結於單向二極體331。當兩側引線321、322 之間之電池單元喪失其功能時’單向二極體331係繞過 (bypass)該電池單元而令相鄰接之電池單元電連結，藉此可 使得1個電池單元之功能降低不對其他電池單元之功能造 成影響。 連結引線321、322與連結電極151、152之部位得為連 結電極151、152全體或中央之一部分。另，連結電極151、 152插入於通孔16卜162時，通孔16卜162之周緣有時會陷 入内側’該情況下，亦可採用於該陷入部嵌合引線32卜322 之方式。 第2 b圖係本發明之單向二極體與第2形態之連結電極 12 201216493 相連結之染料敏化太陽能電池模組之剖面圖。 如第2b圖所示，第2實施例亦與第1實施例相同，其包 含：前面透明基板111與後面透明基板121 ;前面導電層 131、141與後面導電層133、143 ; Ti02多孔質層132、142 與觸媒電極134、144 ;然後尚包含：電解質層136、146 ; 作為絕緣層之密封部135a、135b、145a、145b ;焊接部311 ; 引線321、322 ;及單向二極體331等。 第2b圖之第2實施例與第1實施例不同在於，電連結前 面導電層與後面導電層之連結電極251、252之形態及形成 方法’其結果有時進而需要填滿後面透明電極121之通孔 161、162的過程。 如第2b圖所示，經由形成於後面透明電極121之許多通 孔161、162 ’連結電極251、252插入於密封部135b、145a 之内部空間。於第2實施例，若將軟質之導電性金屬粒(peiiet) 之例如銦（indium)粒插入於通孔161後，從後方加壓，則軟 質之銦粒一面於密封部135b ' 145a之内部空間擴散，一面 形成連結電極。 於連結電極251、252之端部電結合引線321、322。電 結合方式可利用焊接等。在此，若連結電極251、252之端 部深入通孔161、162之内部，則有時難以將連結電極251、 252與引線32卜322相連結。因此，將銦粒插入於通孔161、 162後而加壓時’宜調節粒量或加壓程度，以使得連結電極 251、252之端部位於通孔161、162之開放部附近。引線32卜 322係往後面透明基板121之方向引出，各引線係連結於單 13 201216493 向二極體331。 引線321、322與連結電極251、252之連結部位宜為連 結電極251、252之中央部全體或一部分，又，連結電極25卜 252形成於通孔161、162時’若通孔16卜162之周緣陷入内 側’則亦能夠以該部分來結合連結電極251、252與引線 321、322。 第2b圖之第2實施例係與第2a圖之第1實施例不同，其 不伴隨有熱處理過程。其中，由於銦粒通過通孔161、162 而進入密封部135b、145a之内部空間，因此通孔161、162 有時殘留為空出的空間。若於通孔161、162形成空出的空 間，則宜以填充材料261、262填滿通孔161、162之空出的 空間。填充材料可湘接著劑。接著劑可利賴塑性高分 子膜、壤氧樹脂、紫外線硬化劑等。即便加壓軟質之銦粒， 右通孔161、162被軟質之銦粒所填滿，則不需要填滿通孔 161、162的過程。 第3a、3b、3。圖係說明製造本發明之染料敏化太陽能 電池之過程。如第3a、3b、3c圖所示，染料敏化太陽能電 池係由製造前面基板之過程、製造後面基板之過程、及黏 合前面基板與後面基板之過程等所構成。 第3a圖係說明製造前面基板之過程。 首先，洗淨導電性前面透明基板(S31)e 於已洗淨之導電性前面透明基板，利用雷射來將電極 予以圖案化，形成導電性透明電極(S32)。 於前面導電層上’利用遮罩，採喷霧方式形成逆向電 14 201216493 子防止層（S33) ’於逆向電子防止層上，利用遮罩形成Ti〇2 多孔質層（S34)。於Ti〇2多孔質層上，可利用遮罩追加形成 反射層（S35)。 於未形成逆向電子防止層、Ti〇2多孔質層及反射層之 前面導電層上，形成柵狀形態之集電電極(S36)。於集電電 極上可進一步形成集電電極保護層（S37)。 其後，經過於Ti〇2多孔質層上吸附染料的過程(S38)。 第3 b圖係說明製造後面基板之過程。 如第3b圖所示’於本發明之後面基板之製造過程中， 包含在後面基板形成通孔之過程。 首先，洗淨導電性後面透明基板(s41)。 於已洗淨之導電性後面透明基板，利用雷射來將電極 予以圖案化，形成導電性透明電極(S42)。 於後面透明基板，利用雷射來形成電解液注入孔及連 結電極通邮43)。纽’使得㈣f _狀位置與密封 β之内部m致。又，於形成電解液注人孔及連結電極 通孔時若產錄子’射伴隨有洗淨過程。 八後’利用遮罩’採噴霧方式形成觸媒電極(S44)。於 未形成觸《極之後㈣電層上，形成滅_之集電電 極(S45)。 ;集電電極上可進—步形成集電電極保護層（S46)。 第3c圖係說明黏合前面基板與後面基板之過程。如第 3c圖所不，本發明之基板絲合過程可伴隨如下過程：於 連結電極it狀㈣插入妓電極之過程 ，·及焊接用以將 15 201216493 連結電極與二極體連結之引狀触；紐可依需要而進 步伴隨有填滿連結電極通孔之過程。首先，利用可熱硬 化之樹脂(resin)印刷密封材料(S51)。 配。電池單7〇之圖案化來黏合前面基板與後面基板， 令樹脂熱硬化(S52)。 其後’於連結電極通孔之内部插入連結電極(S53)。連 結電極有時為熱硬化性之導電性金屬，例如糊狀物(pash) 或墨水㈣)形態之銀(Ag)，彻注射H，於連結電極通孔 之内I主人銀糊或銀墨水而填滿於密封部之内部空間。連 結電極可利用軟質之導紐金屬粒(pdlet) ，例如銦(indium) 粒，忒情况下，銦粒係於插入於連結電極通孔的狀態下， 被予以後方加壓’此時，軟質之銦粒擴散於密封部之内部 空間。 當連結電極形成時，使得將連結電極與二極體連結之 引線結合於連結電極(S54)。連結電極與引線之連結可利用 焊接等。 利用軟質粒作為連結電極時，可進一步進行填滿引線 所連結的連結電極之通孔的過程。填充材料可利用接著 劑’接著劑包括熱塑性高分子膜、環氧樹脂、紫外線硬化 劑等。 其後’於電解液注入孔注入電解液(S55)，封住電解液 注入孔（S56)。 於第3c圖之製造過程中，可先注入電解液’其後插入 連結電極。該情況下，有時電解液進入連結電極通孔而腐 201216493 姓電極目此於先注入電解液時，宜先進行封閉連結電極 ^孔之過私’其後注人電解液。被封閉之後面基板之通孔 係為了注人連結電極而再度被開放。 第4a 4b圖係於由4個電池單元所構成的2個染料敏化 太陽能電池模組’其個電池單元附著單向二極體，另 維持不附著單向二極體，一面遮蔽1個電池單元之光電極 面一面測定時所示之電流_電壓曲線。在此，A曲線係不附 著二極體之模組的曲線，B曲線係附著有二極體之模組的曲 線。單向二極體係使用正向電阻380歐姆(Ω)，逆向電阻無 限大者。 太陽能電池之功率效率可藉由一面施加固定電壓，一 面測定電流變化之線圖來評估。於同一電流最大值(Isc)及 電壓最大值(Voc)的狀態下，電流—電壓曲線之折曲部分越 接近連結電流最大值與電壓最大值之長方形，則評估其功 率效率越高。亦即’電流最大值(Isc)、電壓最大值(v〇c)、 與電流-電壓曲線相接之四角形之最大面積（FF : Fill Factor(填充因數))等若有一者上升’則可評估為功率效率已 提升。 第4a圖係於作為比較之2個模組，分別將1個電池單元 遮蔽50%時之電流—電壓曲線。在電流-電壓曲線及下方的 資料中，電壓最大值(Voc)與FF值幾乎無差距，但可確認附 著有單向二極體之模組之電流最大值（1 252)高於不附著單 向二極體之模組之電流最大值（1.118)。該結果可評估為附 著有單向二極體之結果。 17 201216493 第4b圖係於作為比較之2個模組，分別將1個電池單元 遮蔽100%時之電流-電壓曲線。在電流-電壓曲線及下方的 資料中，可確認附著有單向二極體之模組之電流最大值、 電壓最大值、FF係較不附著單向二極體之模組之電流最大 值、電壓最大值、FF大幅增加。尤其是FF的情況，可確認 附著有單向二極體之模組之F F (3 0 · 01)係較不附著單向二極 體之模組之FF(19.72)增加將近2倍。該結果可做出如下結 論：附著有單向二極體時，明確顯示模組之功率效率大為 改善。 以上所說明的實施例係用以說明本發明之技術性思 想，不求限定權利範圍。因此，本發明之權利範圍須藉由 下述申請專利範圍之記載來決定。又，於下述申請專利範 圍所記載、不脫離本發明思想之範圍内，預測若是熟悉該 技藝的人士，均可將本發明思想進行各種修正或變更，該 類修正或變更係包含於本發明之權利範圍内。 【圖式簡單說明】 第1圖係具有後面基板貫穿之連結電極之染料敏化太 陽能電池模組之剖面圖。 第2 a圖係本發明之單向二極體與第1形態之連結電極 相連結之染料敏化太陽能電池模組之剖面圖。 第2 b圖係本發明之單向二極體與第2形態之連結電極 相連結之染料敏化太陽能電池模組之剖面圖。 第3a圖係說明製造前面基板之過程之圖式。 第3b圖係說明製造後面基板之過程之圖式 18 201216493 第3c圖係說明黏合前面基板與後面基板而完成本發明 之染料敏化太陽能電池之過程之圖式。 第4a及4b圖係於由4個電池單元所構成的2個染料敏化 太陽能電池模組，其一對1個電池單元附著單向二極體，另 一維持不附著單向二極體，一面遮蔽1個電池單元之光電極 面一面測定時所示之電流-電壓曲線。 【主要元件符號說明】 111...前面透明基板 261、262...填充材料 121...後面透明基板 311.··焊接部 131、141...前面導電層 32卜322…引線 132、142···Ή02多孔質層 331…單向二極體 133、143…後面導電層 FF...填充因數 134、144...觸媒電極 Isc...電流最大值 135a、135b、145a、145b...密封部 Voc...電壓最大值 136、146…電解質層 S31 〜S38、S41 〜S46、S51〜 151、152、25卜252…連結電極 161、162...通孔 S56...過程 19Ru(etc bpy) 2 (NCS) 22CH3CN type. Here, the etc system (COOEt) 2 or (COOH) 2 is a reactive group which can bond to the surface of the porous membrane (Ti〇2). The catalyst electrodes 134 and 144 are preferably made of platinum, carbon, carbon nanotubes or the like, and have a thickness of about 1 to 300, and the light transmittance is ι 〇 100%. In particular, the original system has good reflectance and is widely used. The electrolyte layers 136, 146 can selectively utilize a liquid electrolyte, an ionic electrolyte, a quasi-solid electrolyte, a polymer electrolyte, a solid electrolyte, or the like. The electrolyte is interposed between the front transparent substrate 111 and the rear transparent substrate 121, and is uniformly dispersed inside the Ti〇2 porous layers 136 and 146. The electrolyte is an idiode/tridiode layer, which functions to receive electrons from the catalyst electrodes 134, 10 201216493 144 by oxidation/reduction and to transfer them to the dye. The sealing portions 135a, 135b, 145a, and 145b as the insulating layer may have been removed from the side of the river surface conductive layer 13b 141 or the rear conductive layers 133, 143, but the sealing portions 135a, 135b, 145a, 145b of the present invention. In order to form a space into which the connection electrodes 151 and 152 to be described later are inserted, it is preferable to form an integral molding. Further, each of the sealing portions 135a, 135b, 145a, and 145b is formed to extend to the front transparent substrate 111 or the rear transparent substrate 121 after the front conductive layer 13b or the rear conductive layers 133, 143 have been removed. In Fig. 2, for example, when one sealing portion 145a is observed, the side end portion of the sealing portion 145a is over the side portion of the front conductive layers 131, 141, and is extended to the front transparent substrate 111, and the sealing portion 145a The other end portion is formed to extend to the upper side surface of the rear conductive layer 14 3 , but is not limited to such a form. The right side can form a closed space by the adjacent sealing portion, and the sealing portion is formed. It can be configured in any form. The space formed by the sealing portions 135b and 145a for insulating the adjacent battery cells is configured to coincide with the positions of the through holes (6) and 162 formed in the transparent substrate i2i. The connection electrode 151 electrically connects the front surface conductive layer 131 of the first battery unit and the second surface unit conductive layer 143 adjacent to the second battery unit. As described above, the "connecting electrode 151 is electrically connected to the front collecting electrode and the rear collecting electrode", and the front collecting electrode is connected to the first battery unit front surface conductive layer 131' and the rear collecting electrode is connected to the second electrode. The battery unit rear surface conductive layer 143 and the connection electrodes 151 and 152 are inserted into the internal spaces of the sealing portions 135b and 145a via the plurality of 201216493 multi-vias 161 and 162 formed in the rear transparent substrate 121. In the first embodiment, when a through-hole 161 is injected with a syringe into a thermosetting conductive metal such as a paste or an ink (Ag), silver paste or silver ink is filled. In the internal space of the sealing portions 135b and 145a, the oven is thermally cured at a temperature of 120 to 17 (at a temperature of TC for 1 to 3 minutes to form the connection electrode 151. Here, the silver paste or the silver ink is along the line. The through holes 161 and 162 are injected. In the figure h, the connection electrode 151' 152 is hardened in the injected state, so that the through holes 16 162 of the rear transparent substrate 121 are filled by the connection electrodes 151 and 152. The ends of the connection electrodes 151 and 152 in the direction of the transparent substrate after the via holes 161 and 162 are electrically coupled to the leads 321 and 322. Here, the manner of electrical bonding can be variously used by soldering or the like. The leads 321 and 322 are transparent to the rear. The direction of the substrate 121 is drawn, and the leads 321 and 322 are connected to the unidirectional diode 331. When the battery cells between the lead wires 321 and 322 lose their functions, the unidirectional diode 331 is bypassed. The battery unit electrically connects the adjacent battery cells, thereby The function of one battery unit is reduced, and the function of the other battery unit is not affected. The portions connecting the leads 321 and 322 and the connection electrodes 151 and 152 are a part of the connection electrodes 151 and 152 or a part of the center. Further, the connection electrodes 151 and 152 are connected. When inserted into the through hole 16 162, the periphery of the through hole 16 162 may be trapped inside. In this case, the fitting portion 32 may be used in the immersed portion. The second b is the present invention. A cross-sectional view of a dye-sensitized solar cell module in which a unidirectional diode is connected to a connection electrode 12 of the second embodiment 201216493. As shown in Fig. 2b, the second embodiment is also the same as the first embodiment, and includes: Front transparent substrate 111 and rear transparent substrate 121; front conductive layers 131, 141 and rear conductive layers 133, 143; Ti02 porous layers 132, 142 and catalyst electrodes 134, 144; then further comprising: electrolyte layers 136, 146; Sealing portions 135a, 135b, 145a, 145b of the insulating layer; soldering portion 311; leads 321, 322; and unidirectional diode 331, etc. The second embodiment of Fig. 2b differs from the first embodiment in that the front side is electrically connected Conductive layer and back guide The form and formation method of the connection electrodes 251 and 252 of the layer may result in a process of filling the via holes 161 and 162 of the transparent electrode 121 later. As shown in FIG. 2b, many of the transparent electrodes 121 are formed through the rear. The through holes 161 and 162' are connected to the internal spaces of the sealing portions 135b and 145a. In the second embodiment, for example, indium particles of a soft conductive metal particle (peiiet) are inserted into the through hole. After 161, when pressed from the rear, the soft indium particles are diffused in the internal space of the sealing portion 135b' 145a to form a connecting electrode. The leads 321 and 322 are electrically coupled to the ends of the connection electrodes 251 and 252. The electric bonding method can utilize welding or the like. Here, when the end portions of the connection electrodes 251 and 252 are deep inside the through holes 161 and 162, it may be difficult to connect the connection electrodes 251 and 252 to the lead wires 32 and 322. Therefore, when the indium particles are inserted into the through holes 161 and 162 and pressurized, it is preferable to adjust the amount of the particles or the degree of pressurization so that the ends of the connecting electrodes 251 and 252 are located near the open portions of the through holes 161 and 162. The leads 32 322 are led out in the direction of the rear transparent substrate 121, and the leads are connected to the single 13 201216493 directional diode 331. It is preferable that the connection portions of the lead wires 321 and 322 and the connection electrodes 251 and 252 are all or part of the central portion of the connection electrodes 251 and 252, and when the connection electrode 25 252 is formed in the through holes 161 and 162, 'if the through hole 16 is 162 It is also possible to bond the connection electrodes 251, 252 and the leads 321, 322 with this portion. The second embodiment of Fig. 2b differs from the first embodiment of Fig. 2a in that it is not accompanied by a heat treatment process. However, since the indium particles enter the internal spaces of the sealing portions 135b and 145a through the through holes 161 and 162, the through holes 161 and 162 may remain as empty spaces. If the vacant spaces are formed in the through holes 161, 162, it is preferable to fill the vacant spaces of the through holes 161, 162 with the filling materials 261, 262. The filling material can be a lubricant. The subsequent agent can be used for plastic high molecular films, soil oxygen resins, ultraviolet curing agents, and the like. Even if the soft indium particles are pressed and the right through holes 161, 162 are filled with the soft indium particles, the process of filling the through holes 161, 162 is not required. 3a, 3b, 3. The drawings illustrate the process of making the dye-sensitized solar cell of the present invention. As shown in Figures 3a, 3b, and 3c, the dye-sensitized solar cell is composed of a process of manufacturing a front substrate, a process of manufacturing a rear substrate, and a process of bonding a front substrate and a rear substrate. Figure 3a illustrates the process of making the front substrate. First, the conductive front transparent substrate (S31) is washed on the cleaned conductive front transparent substrate, and the electrode is patterned by laser to form a conductive transparent electrode (S32). On the front conductive layer, a reverse electricity is formed by spraying, and a 2012-11493 sub-preventing layer (S33)' is formed on the reverse electron-preventing layer, and a Ti〇2 porous layer is formed by a mask (S34). On the Ti〇2 porous layer, a reflective layer can be additionally formed by a mask (S35). A collector electrode of a grid-like shape is formed on the front conductive layer on which the reverse electron-preventing layer, the Ti〇2 porous layer, and the reflective layer are not formed (S36). A collector electrode protective layer (S37) may be further formed on the collector electrode. Thereafter, a process of adsorbing the dye on the porous layer of Ti 2 is performed (S38). Figure 3b illustrates the process of making the back substrate. As shown in Fig. 3b, in the manufacturing process of the back substrate of the present invention, a process of forming a via hole in the rear substrate is included. First, the conductive rear transparent substrate (s41) is washed. The electrode is patterned by laser irradiation on the cleaned conductive back transparent substrate to form a conductive transparent electrode (S42). On the rear transparent substrate, the electrolyte injection hole and the connection electrode are formed by laser irradiation 43). The neon makes the (iv) f _ position and the inner m of the seal β. Further, when the electrolyte injection hole and the connection electrode through hole are formed, the production process is accompanied by a cleaning process. After eight, the catalyst electrode is formed by a masking method (S44). On the electrical layer after the "pole" is not formed, a collector electrode (S45) is formed. The collector electrode may be stepwise formed to form a collector electrode protective layer (S46). Figure 3c illustrates the process of bonding the front substrate to the back substrate. As shown in Fig. 3c, the substrate splicing process of the present invention may be accompanied by a process of inserting a 妓 electrode in the connection electrode (4), and welding a contact for connecting the 15 201216493 connection electrode to the diode. Newcomer progresses as needed with the process of filling the through-holes of the connecting electrodes. First, the sealing material (S51) is printed using a heat-hardenable resin. Match. The battery sheet is patterned to bond the front substrate and the rear substrate to thermally harden the resin (S52). Thereafter, the connection electrode is inserted into the connection electrode through hole (S53). The connecting electrode may be a thermosetting conductive metal, such as silver (Ag) in the form of a paste or ink (four), and is completely injected with H, and is inside the connecting electrode through hole. Fill the inner space of the seal. The connection electrode can be made of a soft pdlet, for example, indium particles. In the case of a crucible, the indium particles are inserted into the through-hole of the connection electrode, and are pressed back. The indium particles diffuse into the inner space of the sealing portion. When the connection electrode is formed, the lead wire connecting the connection electrode and the diode is bonded to the connection electrode (S54). The connection between the connection electrode and the lead wire can be performed by welding or the like. When a soft plasmid is used as the connection electrode, the process of filling the via hole of the connection electrode to which the lead is connected can be further performed. The filler can be made of a binder. The adhesive includes a thermoplastic polymer film, an epoxy resin, an ultraviolet curing agent, and the like. Thereafter, the electrolyte solution (S55) is injected into the electrolyte injection hole to seal the electrolyte injection hole (S56). In the manufacturing process of Fig. 3c, the electrolyte may be injected first and then the connecting electrode may be inserted. In this case, the electrolyte may enter the connecting electrode through-hole and the etched 201216493 surname electrode should be injected into the electrolyte first. The through hole of the surface substrate after being closed is opened again in order to connect the electrodes. 4a 4b is a diagram of two dye-sensitized solar cell modules composed of four battery cells. One of the battery cells is attached to the unidirectional diode, and the unidirectional diode is not attached, and one battery is shielded. The current-voltage curve shown on the side of the photoelectrode surface of the cell. Here, the A curve is not attached to the curve of the module of the diode, and the B curve is attached to the curve of the module of the diode. The unidirectional diode system uses a forward resistance of 380 ohms (Ω), and the reverse resistance is not limited. The power efficiency of a solar cell can be evaluated by applying a fixed voltage on one side and measuring the current change on one side. In the state of the same current maximum (Isc) and voltage maximum (Voc), the closer the bent portion of the current-voltage curve is to the rectangle connecting the maximum value of the current and the maximum value of the voltage, the higher the power efficiency is evaluated. That is, the current maximum value (Isc), the voltage maximum value (v〇c), and the maximum area of the square (FF: Fill Factor) that is in contact with the current-voltage curve, etc., can be evaluated if one rises. The power efficiency has been improved. Figure 4a shows the current-voltage curve when one battery unit is shielded by 50% for the two modules to be compared. In the current-voltage curve and the data below, there is almost no difference between the voltage maximum (Voc) and the FF value, but it can be confirmed that the maximum current (1 252) of the module with the unidirectional diode attached is higher than the non-attachment The maximum current of the module to the diode (1.118). This result can be evaluated as a result of attaching a unidirectional diode. 17 201216493 Figure 4b shows the current-voltage curve when one battery unit is shielded by 100% for the two modules to be compared. In the current-voltage curve and the following data, it is confirmed that the current maximum value, the voltage maximum value of the module to which the unidirectional diode is attached, and the current maximum value of the module in which the FF system is not attached to the unidirectional diode, The maximum voltage and FF increase significantly. Especially in the case of FF, it can be confirmed that the F F (3 0 · 01) of the module to which the unidirectional diode is attached is nearly twice as large as the FF (19.72) of the module to which the unidirectional diode is not attached. This result can be concluded as follows: When a unidirectional diode is attached, it is clearly shown that the power efficiency of the module is greatly improved. The embodiments described above are intended to illustrate the technical idea of the present invention and are not intended to limit the scope of the invention. Therefore, the scope of the invention should be determined by the description of the scope of the claims below. In addition, it is intended that various modifications and changes can be made without departing from the spirit and scope of the invention. Within the scope of the rights. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a dye-sensitized solar cell module having a connection electrode through which a rear substrate is inserted. Fig. 2a is a cross-sectional view showing a dye-sensitized solar cell module in which the unidirectional diode of the present invention is connected to the connection electrode of the first embodiment. Fig. 2b is a cross-sectional view showing the dye-sensitized solar cell module in which the unidirectional diode of the present invention is connected to the connection electrode of the second embodiment. Figure 3a is a diagram illustrating the process of fabricating the front substrate. Fig. 3b is a diagram showing the process of manufacturing the rear substrate. 18 201216493 Fig. 3c is a view showing a process of bonding the front substrate and the rear substrate to complete the process of the dye-sensitized solar cell of the present invention. Figures 4a and 4b are two dye-sensitized solar cell modules composed of four battery cells, one pair of battery cells are attached to the unidirectional diode, and the other is maintained without the unidirectional diode. The current-voltage curve shown when the photoelectrode surface of one of the battery cells is shielded. [Description of main component symbols] 111... front transparent substrate 261, 262... filling material 121... rear transparent substrate 311. · soldering portions 131, 141... front conductive layer 32 322 ... lead 132, 142···Ή02 porous layer 331...unidirectional diodes 133,143...back conductive layer FF...fill factor 134,144...catalyst electrode Isc...current maximum 135a, 135b, 145a, 145b...sealing portion Voc...voltage maximum 136, 146...electrolyte layers S31 to S38, S41 to S46, S51 to 151, 152, 25, 252...connecting electrodes 161, 162...through holes S56.. Process 19