201139615 六、發明說明： 【發明所屬之技術領域】 本發明係有關波長變換材料的技術，特別是有關照射 近紫外光〜藍色光於螢光體而激發，引起發光進行波長變 換，使太陽能電池的效率提昇之技術。 【先前技術】 〇 太陽能電池的量子效率係一般在紫外光〜藍色光的範 圍中，比較於綠色光〜近紅外光之範圍爲低。隨之，在到 達至太陽能電池的光之波長成分之中，經由將紫外光〜藍 色光的波長之光線，波長變換成綠色光〜近紅外光的光線 之時’使太陽能電池之量子效率高的波長範圍的光線增加 ’可提昇太陽能電池的效率。從以往知道有經由光到達至 太陽能電池的路徑中，設置波長變換膜之時，太陽能電池 的效率提昇之情況。 〇 例如’在「專利文獻1」中，作爲波長變換材料而使 用螢光著色劑。另外’在「專利文獻2」中，使用稀土類 錯合物含有ORMOSIL複合體。另外，在「非專利文獻1 」中，使用有機金屬錯合物。但在記載於「非專利文獻1 」之技術及上述的螢光著色劑及有機金屬錯合物中，因耐 久性不充分之故’作爲在長期間之太陽能電池用波長變換 材料之機能的保持則爲困難。另外，亦有有機金屬錯合物 之波長變換量子效率爲低之0.6程度之課題。另外，在「 專利文獻3」中，記載有使用螢光體之太陽能電池用波長 -5- 201139615 變換材料’但在「專利文獻3」中，未記載有具體之效率 提昇量之數値’而在「專利文獻4」中，發電效率之提昇 效果係亦不充分。 以往技術文獻 [專利文獻] [專利文獻1]日本特開2001-7377號公報 [專利文獻2]日本特開2000-327715號公報 [專利文獻3]日本特開2〇03_218379號公報 [專利文獻4]日本特開平7 — 202243號公報 [非專利文獻] [非專利文獻1 ]日本第5 8次錯合物化學討論會預備 稿集 1PF-011 【發明內容】 [發明欲解決之課題] 對於使用有機金屬錯合物於太陽能電池用之波長變換 材料的情況’係有提昇其耐久性之課題。另外，亦有有機 金屬錯合物之波長變換之量子效率爲低之〇 · 6程度之課題 。因此’作爲有將無機系化合物之螢光體作爲太陽能電池 用波長變換材料而使用之方法。但在以往之波長變換材料 之波長變換效率中’未到達至充分提昇太陽能電池之光電 變換效率’而要求更提昇光電變換效率。 本發明係有鑑於上述課題而作爲之構成，其目的爲提 -6- 201139615 供：提昇波長變換材料之波長變換效率，可提昇太陽能電 池之光電變換效率之構成。 [爲解決課題之手段] 在本申請所揭示之發明之中，如簡單地說明代表性之 構成槪要，如以下所述。 種由保遵太陽能電池之封閉材所構成之封閉材薄片 〇 ’其特徵爲對於前述封閉材係混合有螢光體，前述螢光體 係母體材料則含有（Ba、Sr)2Si04、（Ba、Sr、Ca)2Si04、 Ba2Si04、Sr3Si05、（Sr、Ca、Ba)3Si05、 (Ba、Sr、Ca)3MgSi208、Ca3Si207、Ca2ZnSi2〇7、 Ba3Sc2Si3〇12、Ca3Sc2Si3012 任一之封閉材薄片。 另外’作爲其他的螢光體係母體材料爲由 MMgAl10O17所表示之化合物，μ係選自Ba、Sr、Ca之中 任何1種或複數種之元素，作爲發光中心而添加E u、Μ η Ο 之任何一種或複數種之元素爲特徵之封閉材薄片。 另外，作爲經由本發明之其他形態的主要構成，係具 有透明基板與封閉材與太陽能電池單元與後座之太陽能電 池模組。另外，前面玻璃係太陽能電池用之半強化玻璃， 有著具有反射防止膜之情況。一種太陽能電池模組，其特 徵爲於光線到達至太陽能電池單元爲止之路徑中，含有螢 光體，前述螢光體係母體材料則含有（Ba、Sr)2Si〇4、 (Ba、Sr、Ca)2Si〇4、Ba2Si04、Sr3Si05、 (Sr、Ca、Ba)3Si05、（Ba、Sr、Ca)3MgSi208、Ca3Si207、 201139615201139615 VI. Description of the Invention: [Technical Field] The present invention relates to a technique for wavelength conversion materials, in particular to excitation of near-ultraviolet light to blue light in a phosphor, causing luminescence to undergo wavelength conversion, so that solar cells are Technology for efficiency improvement. [Prior Art] 量子 The quantum efficiency of a solar cell is generally in the range of ultraviolet light to blue light, and is relatively low in the range of green light to near infrared light. In the meantime, when the wavelength of the light reaching the solar cell is converted into the light of the green light to the near-infrared light by the light of the wavelength of the ultraviolet light to the blue light, the quantum efficiency of the solar cell is high. Increased light in the wavelength range can increase the efficiency of solar cells. It has been known that the efficiency of a solar cell is improved when a wavelength conversion film is provided in a path through which light reaches a solar cell. For example, in "Patent Document 1", a fluorescent coloring agent is used as a wavelength converting material. Further, in "Patent Document 2", a rare earth complex is used to contain an ORMOSIL composite. Further, in "Non-Patent Document 1", an organic metal complex is used. However, in the technique of "Non-Patent Document 1" and the above-mentioned fluorescent coloring agent and organic metal complex, the durability is insufficient, and the function as a wavelength conversion material for a solar cell for a long period of time is maintained. It is difficult. Further, there is a problem that the wavelength conversion quantum efficiency of the organometallic complex is as low as 0.6. In addition, "Patent Document 3" describes a wavelength of a solar cell using a phosphor -5 - 201139615 conversion material. However, in "Patent Document 3", a specific number of efficiency improvement amounts is not described. In "Patent Document 4", the effect of improving power generation efficiency is also insufficient. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-327715 (Patent Document 3) JP-A-2002-218379 (Patent Document 4) [Non-patent document] [Non-Patent Document 1] Japan's 58th Complex Chemistry Symposium Preparation Draft 1PF-011 [Summary of the Invention] [Problems to be Solved by the Invention] The case where the organometallic complex is used for a wavelength conversion material for a solar cell has a problem of improving its durability. In addition, there is also a problem that the quantum efficiency of the wavelength conversion of the organometallic complex is low. Therefore, there is a method in which a phosphor having an inorganic compound is used as a wavelength conversion material for a solar cell. However, in the wavelength conversion efficiency of the conventional wavelength conversion material, 'the photoelectric conversion efficiency of the solar cell is not sufficiently reached', and it is required to further improve the photoelectric conversion efficiency. The present invention has been made in view of the above problems, and an object thereof is to provide a structure for improving the wavelength conversion efficiency of a wavelength conversion material and improving the photoelectric conversion efficiency of a solar battery. [Means for Solving the Problem] Among the inventions disclosed in the present application, a representative constitutional summary will be briefly described as follows. A closed material sheet comprising a sealing material of a solar cell of the solar cell is characterized in that a fluorescent material is mixed with the sealing material, and the fluorescent material precursor material contains (Ba, Sr) 2Si04, (Ba, Sr). , Ca) 2Si04, Ba2Si04, Sr3Si05, (Sr, Ca, Ba) 3Si05, (Ba, Sr, Ca) 3MgSi208, Ca3Si207, Ca2ZnSi2〇7, Ba3Sc2Si3〇12, Ca3Sc2Si3012. In addition, as another fluorescent system precursor material, it is a compound represented by MMgAl10O17, and μ is selected from any one or a plurality of elements of Ba, Sr, and Ca, and Eu, ΜηΟ is added as an illuminating center. Any one or more of the elements are characterized by a closure sheet. Further, as a main configuration of another aspect of the present invention, a solar battery module having a transparent substrate and a sealing material, and a solar battery unit and a rear seat is provided. In addition, the semi-tempered glass for the front glass-based solar cell has a reflection preventing film. A solar cell module characterized in that a phosphor is contained in a path until light reaches a solar cell, and the fluorescent matrix precursor material contains (Ba, Sr) 2Si〇4, (Ba, Sr, Ca) 2Si〇4, Ba2Si04, Sr3Si05, (Sr, Ca, Ba)3Si05, (Ba, Sr, Ca)3MgSi208, Ca3Si207, 201139615
Ca2ZnSi207、Ba3Sc2Si3012、Ca3Sc2Si3〇12i 任一。 另外’作爲前述太陽能電池模組之螢光體係母體材料 爲由MMgAl1()〇17所表示之化合物，μ係選自Ba、Sr、Ca 之中任何1種或複數種之元素’作爲發光中心而添加E u 、Μη之任何一種或複數種之元素爲特徵之太陽能電池模 組。 [發明效果] 在本發明中’波長變換材料之效率爲高之故，可提昇 太陽能電池之光電變換效率。另外，在本發明中，作爲波 長變換材料而使用螢光體，但螢光體係對於安定性優越之 故’可實現信賴性高的太陽能電池模組。 另外，經由混入波長變換材材料之螢光體於封閉材薄 片之時’可實現生產性優越，光電變換效率高的太陽能電 池模組。 【實施方式】 <太陽能電池模組之構造> 於圖1顯示有本發明之太陽能電池模組的構造。太陽 能電池模組1係由設置於太陽光所入射側之前面玻璃2 ’ 封閉材（透明樹脂）3，太陽能電池單元（太陽能電池元 件）4，及後座5所成，對於前面玻璃2之太陽光所入射 側係形成有反射防止膜6。雖期望有反射防止膜，但亦可 〇 /»\\ -8 - 201139615 前面玻璃2係其成分除了玻璃之外，而如爲聚碳酸酯 ’丙烯酸’聚酯’氟化聚乙烯等不會阻礙太陽光的入射之 透明’亦可使用此等材料的構成。另外，封閉材3係作爲 保護材的作用，呈被覆將光能變換成電能之太陽能電池單 元4地加以配置。另外，作爲封閉材係除了 EVA (乙烯-醋酸乙烯共聚物）之外，亦可使用矽的裝塡材，聚乙烯醇 縮丁醛等。 〇 作爲太陽能電池單元4，可使用單結晶矽太陽能電池 ’多結晶矽太陽能電池’薄膜化合物半導體太陽能電池， 非晶形矽太陽能電池等之各種太陽能電池元件。其太陽能 電池單元4係於太陽能電池模組1內，加以配置1個乃至 複數，加以複數配置之情況係電性地由互連器加以連接。 另外’作爲後座5係爲了具有耐候性，高絕緣性，及強度 ，可作爲金屬層及塑料薄膜層。 波長變換材料7係如圖1所示，可混合於封閉材3而 〇 使用。對於此情況’封閉材3則吸收近紫外光〜藍色光， 構成放出綠色〜近紅外光之波長變換層。另外，將波長變 換膜’與封閉材3 —起製作太陽能電池模組之故，而可將 製造工程簡素化。 另外，前述波長變換層係如存在於至少太陽光入射至 太陽能電池單元4之間即可，如至少位於前面玻璃2之受 光表面及前面玻璃2與太陽能電池單元4之間任一即可。 另外，波長變換層係如可只吸收入射至太陽能電池單元的 光即可之故，至少如存在於可供給對於太陽能電池單元4 _ 9 - 201139615 之變換成太陽光的入射部的光之位置即可，未以與太陽能 電池模組1之表面積相同面積均一地存在亦可。 隨之’作爲太陽能電池模組之構造，除圖1所示之構 成之外’如圖2所示，可於封閉材3之太陽能電池單元側 形成波長變換層8。對於此情況，至從波長變換材料所放 出的光之太陽能電池元件爲止的距離變短，可抑制光的擴 散。 另外，如圖3所示’設置反射防止膜6之情況，可將 波長變換材料7混勻於反射防止膜6而使用。對於此情況 ’係與反射防止膜6 —起製作波長變換膜之故而可將製造 工程作爲簡素化。另外，於未有經由前面玻璃2之紫外光 的吸收之前面玻璃之表面，形成波長變換膜之故，而可將 紫外光波長變換成可視光〜近紅外光。也就是，紫外光則 較波長變換後的光’經由玻璃之吸收爲大之故。 另外’如圖4所示，可於反射防止膜6與前面玻璃2 之間’形成波長變換膜8。對於此情況，於未有經由前面 玻璃2之紫外光的吸收之表面，形成波長變換膜8之故， 可將紫外光波長變換成可視光〜近紅外線。 另外’對於上述之構成而使用集光透鏡9，支持框1 0 ’基板1 1等’如圖5，可作爲集光型太陽能電池而使用 。經由波長變換材料，將能量高之短波長的光變換成能量 低之長波長的光，太陽能電池元件之能帶隙以上之過剩的 能量減少之故，作爲集光型太陽能電池而使用，亦可抑制 太陽能電池元件之溫度上升。 -10- 201139615 如以上’作爲於光到達至太陽能電池之路徑中，設置 含有螢光體之材料的構造之太陽能電池，係考量有混合於 前面玻璃2或封閉材3之材料的方法，於適當的溶媒調配 波長變換材料7而塗佈於所期望處之方法等，如未阻礙在 太陽能電池單元4之太陽光的吸收，未損及波長變換材料 7之機能的形態’亦可爲任何方法。其中，將圖1所示之 波長變換材料7混勻於封閉材3而使用之方法係可將製造 〇 方法簡素化’作爲設置波長變換材料7之方法爲優越。 <作爲波長變換材料之激發端波長、粒徑、添加濃度> 太陽能電池的量子效率係一般從藍色光變爲近紫外光 ’伴隨入射的光的波長變爲短波長而下降。另一方面，作 爲波長變換材料，係使用螢光體的量子效率爲0 · 7 ~0.9程 度之構成。在此所稱的量子效率係以來自對於螢光體之入 射光之螢光體之出射光比例，可經由量子效率測定裝置而 〇 測定。另外，螢光體的發光係同向性，有著未朝向太陽能 電池單元之後方發光的成分。 因此，太陽能電池的量子效率之下降與螢光體的量子 效率及後方發光的比例則存在有經由權衡之激發帶的波長 。圖6係顯示試算對於有太陽光光譜強度之300nm以上 ，使有激發帶之螢光體的長波長側的激發端波長變化情況 之發電電力增加分的結果。在此，激發端波長係指在激發 光譜之長波長側的激發強度開始之波長，作爲顯示成爲激 發光譜之峰値強度的1 0 %之波長。 -11 - 201139615 經由波長變換之發電電力的增加係在量子效率 〇_6〜0·9中，激發端波長則在3 50〜670nm可看到。發電電 力之增加係於激發端波長爲4 3 0〜5 0 0 n m時爲最大。即， 波長變換材料的量子效率如爲〇 . 6 ~ 〇 · 9，由使用激發端波 長爲43〇〜5〇〇nm之範圍的波長變換材料者，可最大限度 提昇太陽能電池之發電電力，而量子效率如爲〇.7〜〇.9， 由使用激發端波長爲450〜50 Onm之範圍的波長變換材料 者’可最大限度提昇太陽能電池之發電電力。另外，對於 波長變換材料之量子效率爲0 · 7以上的情況，即使使用激 發端波長更爲410〜600nm之構成，亦可較使用以往之有 機金屬錯合物（量子效率爲0 · 6程度）之波長變換的情況 而提昇太陽能電池之發電電力。 另一方面，在螢光體中，除了經由上述之後方發光的 損失之外，亦有經由光學散亂之損失，其程度係關係於粒 徑與添加濃度。波長變換材料之粒徑與光散亂強度的關係 係將太陽光的波長作爲5 0 0 nm時，光散亂強度係經由米 氏散亂，在其一半的25〇nm之粒徑成爲最大。圖7係顯 示光散亂強度與粒徑之關係。在較2 5 Onm爲小之粒徑中 ，散亂強度係由相干散亂所支配的粒徑越小，散亂強度係 越減少，另外，在較2 5 Onm爲大之粒徑中，由幾何光學 散亂所支配，粒徑越大，散亂強度係越下降。粒徑爲小時 ，光散亂強度係下降，但螢光體的發光強度則下降。另外 ，粒徑過大時，必須增加添加濃度，有損封閉材的機能。 對於粒徑的設定係必須考慮此等情況，但1 〇nm〜20 // m之 -12- 201139615 粒徑範圍則爲適當。 接著’作爲對於波長變換材料之封閉材中的添加濃度 ’在太陽光入射側，入射之光子到達至太陽能電池單元爲 止’至少存在有1個螢光體粒子，於混合於封閉材中之螢 光體’均勻分布太陽光爲佳。 如添加濃度過剩，光學散亂則增加，另外，添加濃度 過少時’未進行波長變換而增加穿透的光。因此，平均粒 0 徑2.3 " m之螢光體的情況之添加濃度係成爲2重量％。 另外’平均粒徑爲5 · 8 # m之螢光體的情況之添加濃度係 成爲5重量％。另外，對於平均粒徑爲ι.2μιη之螢光體 的情況’係添加濃度成爲1重量％。隨之，對於螢光體的 平均粒徑爲1〜5 # m之情況，添加濃度係成爲！〜5重量％ 。也就是’當排列粒徑大的螢光體時，螢光體之重量％係 變大。但此係計算螢光體之必要量的結果，在此量的前後 存在有最佳濃度。 〇 隨之，如將螢光體之平均粒徑作爲A( y m)，最佳濃 度範圍之B(重量％ )係從最佳濃度2A/2.3之1/200倍程度 開始出現效果，至1 〇倍程度可看到效果。隨之，螢光體 的濃度係在0.004AS B s 8.7A之範圍爲良好，如考慮光的 抑制及光散亂，更加爲在從最佳濃度2 A/2.3之1 /1 〇 〇倍 程度至5倍程度之範圍，波長變換的效果爲高。隨之，螢 光體的濃度係在0.008ASBS4.3A之範圍成爲最佳。 <波長變換材料之選定> -13- 201139615 作爲波長變換材料，可將5 0 0 nm以下之近紫外光〜 藍色光，光變換成500nm〜llOOnm之綠色光〜近紅外光而 入射至太陽能電池單元之材料爲佳。 特別是’於有著太陽光光譜強度之300nm以上有激 發帶，量子效率爲0.7以上’激發端波長位於410〜60Onm 之材料爲佳。特別是激發端波長位於4 3 0 ~ 5 0 0 n m之材料 爲最佳。更且，從亮度壽命及耐濕性的點，使用於各種顯 示器，燈’及白色LED等之無機螢光體材料爲佳。但限 定於激發帶分布於近紫外光〜藍色光之構成。在本發明中 ’從如此之觀點，激發帶存在於近紫外光〜藍色光，更且 選定光變換效率高的螢光體材料組成。然而，螢光體係在 螢光燈，陰極射線管，電漿顯示裝置等，有著使用非常長 之實績，確立信賴性之構成爲多。 (波長變換材料1 ) 使用於本發明之波長變換材料之螢光體係母體材料則 由M x S i y Ο z所代表之化合物，Μ係選自鋇，緦，鈣，鎂， 鋅’銃的群任一種或複數種之元素，其化合物的組成比係 2^x^5' 4^z^12的範圍。另外，其化合物 係作爲例而可舉出（Ba、Sr)2Si〇4、（Ba、Sr、Ca)2Si04、 Ba2Si04、Sr3Si〇5、（Sr、Ca、Ba)3Si05、 (Ba、Sr、Ca)3MgSi2〇8、Ca3Si2〇7，Ca2ZnSi207、 Ba3Sc2Si30]2、Ca3Sc2Si3Ol2。另外，作爲發光中心而添加 的賦活劑則選自銪，锰，铈的群之任一種或複數種的元素 -14- ΟAny of Ca2ZnSi207, Ba3Sc2Si3012, Ca3Sc2Si3〇12i. Further, 'the fluorescent material precursor material of the solar cell module is a compound represented by MMgAl1()〇17, and μ is selected from any one or a plurality of elements of Ba, Sr, and Ca' as a luminescent center. A solar cell module characterized by adding any one or a plurality of elements of E u and Μη. [Effect of the Invention] In the present invention, the efficiency of the wavelength converting material is high, and the photoelectric conversion efficiency of the solar cell can be improved. Further, in the present invention, a phosphor is used as the wavelength converting material, but the fluorescent system is excellent in stability, and a highly reliable solar cell module can be realized. Further, the solar cell module having excellent productivity and high photoelectric conversion efficiency can be realized by the phosphor incorporated in the material of the wavelength conversion material at the time of the sealing material sheet. [Embodiment] <Structure of Solar Cell Module> Fig. 1 shows the structure of a solar cell module of the present invention. The solar cell module 1 is formed by a glass 2' sealing material (transparent resin) 3, a solar cell unit (solar cell element) 4, and a rear seat 5 disposed on the side on which the sunlight is incident, and the sun for the front glass 2 An anti-reflection film 6 is formed on the incident side of the light. Although an anti-reflection film is desired, it can also be 〇/»\\ -8 - 201139615. The front glass 2 is a component other than glass, but the polycarbonate 'acrylic' polyester fluorinated polyethylene does not hinder. The transparency of the incident sunlight can also be made using these materials. Further, the sealing member 3 is disposed as a protective material and is disposed so as to cover the solar battery unit 4 that converts light energy into electric energy. Further, as the sealing material, in addition to EVA (ethylene-vinyl acetate copolymer), a crucible material, polyvinyl butyral or the like may be used. 〇 As the solar battery unit 4, various solar battery elements such as a single crystal germanium solar cell, a polycrystalline germanium solar cell, a thin film compound semiconductor solar cell, and an amorphous germanium solar cell can be used. The solar battery cells 4 are housed in the solar battery module 1, and are disposed in one or more plural, and are electrically connected by interconnectors in a plurality of configurations. Further, as the rear seat 5, it can be used as a metal layer or a plastic film layer in order to have weather resistance, high insulation properties, and strength. The wavelength converting material 7 is as shown in Fig. 1, and can be mixed with the sealing material 3 and used. In this case, the closing material 3 absorbs near-ultraviolet light to blue light, and constitutes a wavelength conversion layer that emits green to near-infrared light. Further, the wavelength conversion film ' is combined with the sealing material 3 to produce a solar cell module, and the manufacturing process can be simplified. Further, the wavelength conversion layer may be present between at least the solar light entering the solar cell unit 4, such as at least between the light receiving surface of the front glass 2 and the front glass 2 and the solar battery cell 4. Further, the wavelength conversion layer may absorb only light incident on the solar cell, and at least may exist at a position where light which can be supplied to the incident portion of the solar cell 4 _ 9 - 201139615 converted into sunlight is present. However, it may not be uniformly present in the same area as the surface area of the solar cell module 1. Then, as the structure of the solar cell module, except for the configuration shown in Fig. 1, the wavelength conversion layer 8 can be formed on the side of the solar cell of the sealing material 3 as shown in Fig. 2 . In this case, the distance from the solar cell element of the light emitted from the wavelength converting material is shortened, and the light diffusion can be suppressed. Further, as shown in Fig. 3, when the anti-reflection film 6 is provided, the wavelength conversion material 7 can be mixed and used in the anti-reflection film 6. In this case, the wavelength conversion film is formed together with the anti-reflection film 6, and the manufacturing process can be simplified. Further, the wavelength conversion film is formed on the surface of the front glass before the absorption of the ultraviolet light through the front glass 2, and the wavelength of the ultraviolet light can be converted into visible light to near-infrared light. That is, the ultraviolet light is larger than the absorption of the wavelength-converted light by the glass. Further, as shown in Fig. 4, the wavelength conversion film 8 can be formed between the anti-reflection film 6 and the front glass 2. In this case, the wavelength conversion film 8 is formed on the surface which is not absorbed by the ultraviolet light of the front glass 2, and the ultraviolet light wavelength can be converted into visible light to near infrared light. Further, the use of the collecting lens 9 for the above configuration, the support frame 10' substrate 1 1 and the like can be used as a concentrating solar cell as shown in Fig. 5 . The light-converting material converts light having a short wavelength of high energy into light having a long wavelength of low energy, and the excess energy of the energy band gap of the solar cell element is reduced, so that it can be used as a concentrating solar cell. The temperature rise of the solar cell element is suppressed. -10- 201139615 As above, as a solar cell having a structure in which a material containing a phosphor is provided in the path of light reaching a solar cell, a method of mixing the material of the front glass 2 or the sealing material 3 is considered as appropriate. The method of applying the wavelength conversion material 7 to the desired portion of the solvent, and the like, without damaging the absorption of sunlight by the solar cell 4, without impairing the function of the wavelength conversion material 7 may be any method. Here, the method of mixing the wavelength converting material 7 shown in Fig. 1 to the sealing material 3 can simplify the method of manufacturing the ’ method as a method of providing the wavelength converting material 7. <Excitation end wavelength, particle diameter, and addition concentration of the wavelength conversion material> The quantum efficiency of the solar cell generally changes from blue light to near-ultraviolet light. The wavelength of the incident light decreases to a short wavelength. On the other hand, as the wavelength converting material, the quantum efficiency of the phosphor is from 0. 7 to 0.9. The quantum efficiency referred to herein is measured by a quantum efficiency measuring device using the ratio of the emitted light from the phosphor of the incident light to the phosphor. Further, the phosphor emits light in the same direction and has a component that does not emit light toward the rear of the solar cell. Therefore, there is a wavelength of the excitation band which is traded by the decrease in the quantum efficiency of the solar cell and the ratio of the quantum efficiency of the phosphor to the rear luminescence. Fig. 6 is a graph showing the results of trial calculation for the increase in the generated power of the excitation end wavelength on the long wavelength side of the phosphor having the excitation band for 300 nm or more of the spectral intensity of the solar light. Here, the excitation end wavelength means a wavelength at which the excitation intensity on the long wavelength side of the excitation spectrum starts, and is a wavelength showing 10% of the peak intensity of the excitation spectrum. -11 - 201139615 The increase in power generated by wavelength conversion is in the quantum efficiency 〇_6~0·9, and the excitation end wavelength is seen at 3 50~670nm. The increase in power generation is maximized when the excitation end wavelength is 4 3 0 to 5 0 0 n m. That is, the quantum efficiency of the wavelength conversion material is 〇. 6 ~ 〇·9, and the wavelength conversion material having a wavelength of 43 〇 to 5 〇〇 nm at the excitation end can be used to maximize the power generation of the solar cell. The quantum efficiency is 〇.7~〇.9, and the wavelength conversion material using the excitation end wavelength of 450~50 Onm can maximize the power generation of the solar cell. Further, in the case where the quantum efficiency of the wavelength conversion material is 0.7 or more, even if the wavelength of the excitation end is more than 410 to 600 nm, the conventional organic metal complex (the quantum efficiency is about 0.6) can be used. The power generation of the solar cell is increased by the wavelength conversion. On the other hand, in the phosphor, in addition to the loss of light emitted through the latter side, there is a loss due to optical scattering, which is related to the particle diameter and the added concentration. The relationship between the particle size of the wavelength conversion material and the light scattering intensity is such that when the wavelength of sunlight is 500 nm, the light scattering intensity is dispersed by Mie, and the particle size at half of 25 〇 nm is maximized. Figure 7 shows the relationship between the intensity of light scattering and the particle size. In the particle size smaller than 2 5 Onm, the scattered intensity is smaller as the particle size governed by the coherent scattering, and the scattered intensity is decreased. In addition, in the particle size larger than 2 5 Onm, The geometric optical scattering is dominated, and the larger the particle size, the lower the scattered intensity. When the particle size is small, the light scattering intensity decreases, but the luminescence intensity of the phosphor decreases. In addition, when the particle size is too large, it is necessary to increase the added concentration to impair the function of the sealing material. For the setting of the particle size, it is necessary to consider such a situation, but the particle size range of -12-201139615 of 1 〇nm~20 // m is appropriate. Then, 'as the additive concentration in the sealing material for the wavelength conversion material', on the incident side of the sunlight, the incident photons reach the solar cell unit, 'at least one phosphor particle exists, and the fluorescence is mixed in the sealing material. The body's uniform distribution of sunlight is preferred. If the concentration is excessively added, the optical scattering increases, and when the concentration is too small, the light that has not undergone wavelength conversion increases the penetration. Therefore, the addition concentration in the case of the phosphor having an average particle diameter of 2.3 " m is 2% by weight. Further, in the case where the phosphor having an average particle diameter of 5 · 8 # m is added, the concentration is 5% by weight. Further, in the case of a phosphor having an average particle diameter of 1⁄2 μm, the concentration was 1% by weight. In the case where the average particle diameter of the phosphor is 1 to 5 # m, the concentration is added! ~5 wt%. That is, when the phosphor having a large particle diameter is arranged, the weight % of the phosphor is increased. However, this is the result of calculating the necessary amount of the phosphor, and there is an optimum concentration before and after this amount. 〇 , , , , , , 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤 萤The degree can be seen. Accordingly, the concentration of the phosphor is good in the range of 0.004 AS B s 8.7 A, such as considering the suppression of light and light scattering, and is more than 1 / 1 of the optimum concentration of 2 A / 2.3. In the range of up to 5 times, the effect of wavelength conversion is high. Accordingly, the concentration of the phosphor is preferably in the range of 0.008 SABS 4.3A. <Selection of wavelength conversion material> -13- 201139615 As a wavelength conversion material, near-ultraviolet light to blue light of 500 nm or less can be converted into green light to near-infrared light of 500 nm to 110 nm and incident on solar energy. The material of the battery unit is preferred. In particular, a material having an excitation band of 300 nm or more having a spectral intensity of sunlight and a quantum efficiency of 0.7 or more and having an excitation end wavelength of 410 to 60 nm is preferable. In particular, materials having an excitation end wavelength of 4 3 0 to 500 nm are preferred. Further, from the viewpoints of brightness life and moisture resistance, it is preferably used for various display devices, such as inorganic phosphor materials such as lamps and white LEDs. However, it is limited to the formation of the excitation band distributed in the near-ultraviolet light to the blue light. In the present invention, from this point of view, the excitation band is present in the near-ultraviolet light to the blue light, and the phosphor material having a high light conversion efficiency is selected. However, the fluorescent system has a very long history of using fluorescent lamps, cathode ray tubes, and plasma display devices, and has a strong reliability. (Wavelength Conversion Material 1) The fluorescent system precursor material used in the wavelength conversion material of the present invention is a compound represented by M x S iy Ο z, and the lanthanide series is selected from the group consisting of lanthanum, cerium, calcium, magnesium, and zinc lanthanum. Any one or more of the elements, the composition ratio of the compound is in the range of 2^x^5' 4^z^12. Further, examples of the compound include (Ba, Sr)2Si〇4, (Ba, Sr, Ca) 2Si04, Ba2Si04, Sr3Si〇5, (Sr, Ca, Ba) 3Si05, (Ba, Sr, Ca). 3MgSi2〇8, Ca3Si2〇7, Ca2ZnSi207, Ba3Sc2Si30]2, Ca3Sc2Si3Ol2. Further, the activator added as the luminescent center is selected from any one of a group of cerium, manganese, lanthanum or a plurality of elements -14- Ο
201139615 。以下’將此等之螢光體的幾個測定例示於以τ 作爲波長變換材料而使用添加銪之平均粒 之（Ba、Sr)2Si04 : Eu螢光體。將此螢光體之德 發光光譜示於圖8° 300nm至500nm，激發帶貝! 外，在太陽能電池之 3〇〇nm〜500nm之範圍的內 率係較在綠色528nm之內部量子效率爲低之故 用（Ba、Sr)2Si04: Eu螢光體而進行波長變換之 昇太陽能電池之光電變換效率。 另外，作爲波長變換材料而使用添加銪之 16/zm之Sr3Si〇5: Eu螢光體。將此螢光體之潔 發光光譜示於圖9。300nm至580nm，激發帶貝 外，在發光光譜中，於 580nm可看到發光峰値 換之量子效率係73%。在太陽能電池之3 00nm~ 範圍的內部量子效率係較在橙色5 8 Onm之內部 爲低之故，經由使用Sr3Si05 : Eu螢光體而進行 之時，可提昇太陽能電池之光電變換效率。 另外，作爲波長變換材料而使用添加铈之 15//m之Ba3Sc2Si3012: Ce螢光體。將此螢光體 譜及發光光譜示於圖10。300nm至500nm，激 大。另外，在發光光譜中，於51 Onm可看到發 波長變換之量子效率係 75% 。在太陽倉 3 00nm〜50〇nm之範圍的內部量子效率係較在綠 之內部量子效率爲低之故，經由使用Ba3Sc2Si3C 光體而進行波長變換之時，可提昇太陽能電池之 徑 1 5 " m 發光譜及 丨擴大。另 部量子效 ，經由使 時，可提 平均粒徑 發光譜及 擴大。另 。波長變 ，5 8 0 nm 之 量子效率 波長變換 平均粒徑 之激發光 發帶則擴 光峰値。 含電池之 色 5 1 Onm : Ce 螢 光電變換 -15- 201139615 效率。 在此’使用於本發明之波長變換材料的螢光體係母體 材料則由MAlSiN：s所代表之化合物，Μ係鋇，緦，鈣， 鎂的任一種或複數種之元素。另外，其化合物係作爲例可 舉出CaAlSiN3、（Sr、Ca)AlSiN3。另外’作爲發光中心而 添加的賦活劑爲銪。 作爲波長變換材料而使用添加銪之平均粒徑1 〇 # Π! 之CaAlSiNr EU螢光體。將此螢光體之激發光譜及發光 光譜示於圖1 1。3 OOnm至 600nm，激發帶則擴大。另外 ，在發光光譜中，於 625nm可看到發光峰値。波長變換 之量子效率係 79%。300nm〜600nm之範圍的太陽能電池 之內部量子效率係較在紅色625nm之內部量子效率爲低 之故’經由使用CaAlSiN3:Eu螢光體而進行波長變換之 時，可提昇太陽能電池之光電變換效率。 另外’作爲波長變換材料而使用添加銪之平均粒徑 10/zm之（Sr、Ca)AlSiN3: Eu螢光體。將此螢光體之激發 光譜及發光光譜示於圖1 2。300nm至6〇Onm，激發帶則 擴大。另外’在發光光譜中，於610nm可看到發光峰値 。波長變換之量子效率係80%。在300nm~6〇Onm之範圍 的太陽能電池之內部量子效率係較在紅色610nm之內部 量子效率爲低之故，經由使用（Sr、Ca)AlSiN3 : Eu螢光體 而進行波長變換之時，可提昇太陽能電池之光電變換效率 -16 - 201139615 (波長變換材料2 ) 力外，作爲螢光體，可使用由MMgAl1Q〇17所代表之 化合物。在此’ M係選自Ba、Sr、Ca之中任一種或複數 種之元素。 作爲波長變換材料而使用添加銪與錳之平均粒徑5 # m之（Ba、Ca)MgAllQ〇17: Eu、Mn螢光體。接著，對於使 用於本發明之（Ba、ca)MgAl1()017: Eu、Μη綠色發光螢光 Ο 體之製造方法加以敘述。螢光體原料係使用BaC03、 CaC03 MgC〇3、a1203、E112O3、及 MnC03。另外，作爲 助溶劑而使用AIF3。各原料之混合量係如以下。201139615. Hereinafter, several measurement examples of the phosphors of the above are shown in the case of using τ as a wavelength conversion material and using (Ba, Sr) 2Si04 : Eu phosphor added with an average particle of ruthenium. The luminescence spectrum of the phosphor is shown in Fig. 8° 300nm to 500nm, and the excitation band is outside. The internal rate in the range of 3〇〇nm to 500nm of the solar cell is lower than the internal quantum efficiency in the green 528nm. Therefore, the photoelectric conversion efficiency of the solar cell of the wavelength conversion is performed using (Ba, Sr) 2Si04: Eu phosphor. Further, as the wavelength conversion material, a 16/zm Sr3Si〇5: Eu phosphor to which ruthenium was added was used. The clean luminescence spectrum of this phosphor is shown in Fig. 9. From 300 nm to 580 nm, the excitation band is outside, and in the luminescence spectrum, the luminescence peak at 580 nm is seen to be 73%. Since the internal quantum efficiency in the range of 300 nm from the solar cell is lower than that inside the orange 5 8 Onm, the photoelectric conversion efficiency of the solar cell can be improved by using the Sr3Si05 : Eu phosphor. Further, as the wavelength conversion material, a Ba3Sc2Si3012: Ce phosphor to which 15/m of ruthenium was added was used. This phosphor spectrum and luminescence spectrum are shown in Fig. 10. From 300 nm to 500 nm, it is excited. In addition, in the luminescence spectrum, the quantum efficiency of the wavelength conversion is 75% at 51 Onm. The internal quantum efficiency in the range of 3 00 nm to 50 〇 nm in the solar cell is lower than the internal quantum efficiency in the green, and the wavelength of the solar cell can be improved by wavelength conversion using the Ba3Sc2Si3C light body. m hair spectrum and 丨 expansion. The other quantum effect, through the time, can be used to extract the average particle size spectrum and expand. Another. The wavelength is changed, the quantum efficiency of 580 nm, the wavelength conversion, the average particle size of the excitation light, and the excitation band is the peak of fluorescence. Battery-containing color 5 1 Onm : Ce Firefly photoelectric conversion -15- 201139615 Efficiency. Here, the fluorescent host material used in the wavelength converting material of the present invention is a compound represented by MAlSiN:s, an element of any one or more of lanthanum, cerium, calcium, and magnesium. Further, examples of the compound thereof include CaAlSiN3 and (Sr, Ca)AlSiN3. Further, the activator added as a luminescent center is ruthenium. As the wavelength conversion material, a CaAlSiNr EU phosphor having an average particle diameter of 1 〇 # Π is added. The excitation spectrum and the luminescence spectrum of this phosphor are shown in Fig. 11. From 00 nm to 600 nm, the excitation band is enlarged. Further, in the luminescence spectrum, the luminescence peak 可 was observed at 625 nm. The quantum efficiency of wavelength conversion is 79%. The internal quantum efficiency of the solar cell in the range of 300 nm to 600 nm is lower than the internal quantum efficiency of 625 nm in red. When the wavelength conversion is performed by using the CaAlSiN3:Eu phosphor, the photoelectric conversion efficiency of the solar cell can be improved. Further, as the wavelength converting material, (Sr, Ca)AlSiN3: Eu phosphor having an average particle diameter of 10/zm added with ruthenium was used. The excitation spectrum and the luminescence spectrum of this phosphor are shown in Fig. 12. From 300 nm to 6 〇 Onm, the excitation band is enlarged. Further, in the luminescence spectrum, the luminescence peak 可 was observed at 610 nm. The quantum efficiency of wavelength conversion is 80%. When the internal quantum efficiency of the solar cell in the range of 300 nm to 6 〇 Onm is lower than the internal quantum efficiency of 610 nm, the wavelength conversion can be performed by using the (Sr, Ca)AlSiN3 : Eu phosphor. Increasing the photoelectric conversion efficiency of a solar cell-16 - 201139615 (wavelength conversion material 2) In addition to the force, a compound represented by MMgAl1Q〇17 can be used as the phosphor. Here, the 'M system' is selected from any one of Ba, Sr, and Ca, or a plurality of elements. As the wavelength conversion material, (Ba, Ca) MgAllQ〇17: Eu, Mn phosphor having an average particle diameter of 5 # m of lanthanum and manganese was used. Next, a method for producing the (Ba, ca) MgAl1() 017: Eu, Μn green luminescent phosphor of the present invention will be described. As the phosphor raw material, BaC03, CaC03 MgC〇3, a1203, E112O3, and MnC03 were used. Further, AIF3 was used as a co-solvent. The mixing amount of each raw material is as follows.
BaC03 ··· 0.8 1 4gBaC03 ··· 0.8 1 4g
CaC〇3··. 0.013g MgC〇3_·· 〇.274g AI2O3··· 2.549g Eu2〇3"* 〇.132g MnC〇3·.. 0.201g AIF3··· 0.004gCaC〇3··. 0.013g MgC〇3_·· 〇.274g AI2O3··· 2.549g Eu2〇3"* 〇.132g MnC〇3·.. 0.201g AIF3··· 0.004g
BaC03係作爲Ca及Eu則置換Ba之構成，作成唯Ca 及Eu之份量少的量。另外，Eu濃度係作爲l5mol%，Μη 濃度係作爲3 5 m ο 1 %。於以硏鉢乾式混合原料之後，於氧 化鋁坩堝塡充原料’以管狀爐145〇°C，以N2-H2還原環 境（H2濃度2 % ) 3小時，進行燒成。將所得到之燒成物 揉開’得到作爲目的之（Ba、Ca)MgAl|〇〇i7: Eu、Μη綠色 發光螢光體（[Ca] = 2.6mol%) ° -17- 201139615 將此螢光體之激發光譜及發光光譜示於圖13。當看 激發光譜時’至300nm〜460nm’於寬廣範圍，激發帶則 擴大。如此’激發帶爲寬之情況係因添加有Eu之故。另 外’當看發光光譜時’於515nm有著發光的峰値，半値 寬度爲窄’顯不尖銳的發光。其發光係經由Mn之構成， 產生從Eu至Mn之能量移動。在太陽能電池之 300nm〜460nm之範圍的量子效率係一·般較在綠色515nm 之里子效率爲低之故’經由使用（Ba、Ca)MgAli〇〇i7: Eu 、Μη螢光體而進行波長變換之時，可提昇太陽能電池之 光電變換效率。 在（Ba、Ca)MgAl10O17: Eu、Μη 螢光體中，將使 Ca 濃度變化之試料的3 65nm激發的發光峰値強度（515nm) 相對値示於圖14。（Ba、Ca)MgAl1()017: Eu、Μη螢光體 之發光峰値強度係經由添加C a之時，較Β a Μ g A1, 〇 Ο , 7 : Eu、Μη螢光體爲增加。Ca係經由O.Olmol%程度之極微 量的添加而產生效果。 由圖1 4，在C a濃度係較7 m ο 1 %爲小的範圍，相對亮 度則超過1〇〇。隨之，Ca濃度係較0.01 mol%爲大而較 9mol%爲小之範圍爲適當，更理想係較 〇.8mol%爲大而 較4mol%以下之範圍爲適當。經由將Ca濃度作爲lmol %之時，相對發光峰値強度係比較於BaMgAl1Q017 : Eu、 Μη螢光體而提昇6%。 另外，製作（Ba、Sr)MgAl1G017: Eu、Μη螢光體’測 定3 6 5nm激發的發光峰値強度。Sr係經由0.01 mol%程度 -18- 201139615 之極微量的添加而產生效果。由圖14’在Sr濃度係較 9 m ο 1 %爲小的範圍，相對亮度則超過1 〇 〇。隨之’ S r濃度 係較O.Olmol%爲大而較9mo 1 %爲小之範圍爲適當’更理 想係較〇.8mol%爲大而較4m〇l%以下之範圍爲適當。 在圖14中，更增加Sr的量，在16mol%〜18mol%中 ，相對亮度係超過1 〇〇。隨之，使用此範圍之Sr的量， 亦可提昇效果。經由將Sr濃度作爲lmol%之時，相對發 ζ) 光峰値強度係比較於BaMgAl1()017 : Eu、Μη螢光體而提 昇4 %。 另外，同樣作爲製作（Ba、Sr、Ca)MgAl1()〇17 : Eu、 Μη螢光體，測定3 65nm激發的發光峰値強度。如圖14 所示，Ca濃度係固定爲2.6mol%，使Sr的濃度變化而評 估相對亮度。此情況，由圖1 4，在S r的量較8 m ο 1 %爲低 的範圍，相對亮度則超過1 〇 〇，效果出現。當更增加S r 的濃度時，在Sr的濃度爲14mol%〜21mol%之範圍，相 〇 對亮度則超過1 00。另外，如圖14所示，經由將Ca濃度 作爲2.6mol%，將Sr濃度作爲lmol%之時，相對發光峰 値強度係比較於BaMgAhoO”： Eu、Μη螢光體而可提昇 7%。 如此，經由將（Ba、Sr)MgAl1()〇17 : eu、Μη、 (Ba、Ca)MgAl10O17: Eu、Μη、及（Ba、Sr、Ca)MgAli〇〇i7 :Eu、Mn之螢光體作爲波長變換材料而設置於太陽能電 池面板之時’可提昇太陽能電池之光電變換效率。 如以上’在本發明所使用之螢光體係激發波長帶存在 -19- 201139615 於300nm以上’且激發端波長存在於4 10〜600nm之範圍 ’且量子效率係爲高的0.7以上。隨之，可提昇太陽能電 池之發電效率。 另外’使用於本發明之螢光體之平均粒徑係l〇nm〜20 # m。在此，螢光體之平均粒徑係可規定成以下。作爲調 查粒子（螢光體粒子）之平均粒徑的方法，有著以粒度分 布測定裝置而測定之方法’及以電子顯微鏡直接觀察之方 法等。 當將以電子顯微鏡調查之情況舉例時，平均粒徑係可 如以下加以算出。將粒子的粒徑之變量（…、0.8〜丨2 #m、1·3 〜1.7"m、1.8 〜2.2#«1、…、6.8 〜7.2"m、7.3 〜7 · 7 // m、7.8〜8 · 2 /z m、…等）之各區間，以階級値（ …、l.〇//m、1.5/zm、2.0/zm.....7.0/zm、7.5/zm、 8_0//m'…）表不，將此作爲Xi。並且，如將以電子顯微 鏡所觀察到之各變量的度數’作爲以fi表示，平均値a 係如以下所表示。 A=lxj f χ/Ί. \ } = f 但Σ f, = N。經由本發明之螢光體係激發帶波長作爲 波長變換材料爲適合之故’作爲太陽能電池用波長變換材 料，可得到優越之效果。 <太陽能電池模組之製作1 > 接著，使用前述波長變換材料而製作太陽能電池模組 。於透明樹脂（EVA )少量添加有機過氧化物，交聯助劑 -20- 16 201139615 及黏著提昇材，以〇. 1重量％之比例，混合平均粒徑 〆m之Sr3Si05 : Eu螢光體，使用加熱至8 0°C之滾輪 機加以混勻之後，使用沖壓機而夾持於2片之聚乙烯 二甲酸酯間，製作將厚度〇.5mm之EVA爲主成分之 材3。 接著，將其封閉材3自然冷卻至室溫，剝下聚乙 苯二甲酸酯薄膜，與前面玻璃2，太陽能電池單元4 0 座5同時，如圖1加以層積，以設定成1 50°C之真空 裝置加以預備壓著。將預備壓著之層積物，以1 5 5 t 烤器進行30分鐘加熱，進行交聯及黏著而製作太陽 池模組1。在本發明中，作爲波長變換材料而使用激 之適合的螢光體，因更加使用光變換效率高的波長變 料之故，太陽能電池模組的電流量大，比較於未使用 變換材料之情況，電流量增加5 %。另外，螢光體之 壽命係比較於使用有機金屬錯合物之情況而提昇。 〇 接著，作爲波長變換材料而使用平均粒徑1 Onm nm之Sr3Si〇5: Eu螢光體，與前述太陽能電池模組 地製作，測定其電流量。在本發明中，作爲波長變換 而使用激發帶之適合的螢光體，因更加使用光變換效 的波長變換材料之故，太陽能電池模組的電流量大， 於未使用波長變換材料之情況，電流量增加5%。螢 之平均粒徑爲小的l〇nm〜lOOnm之故，螢光體的亮度 ’但散亂亦爲低之故，亦可使電流量增加5 %。 接著’作爲波長變換材料而使用平均粒徑50nm. 硏磨 對苯 封閉 烯對 ，後 層壓 之烘 能電 發帶 換材 波長 亮度 ~ 100 同樣 材料 率高 比較 光體 爲低 -21 - -250 201139615 nm之SQSiO5 : Eu螢光體，與前述太陽能電池模組同樣 地製作’測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 的波長變換材料之故’太陽能電池模組的電流量大，比較 於未使用波長變換材料之情況，電流量增加6 %。螢光體 的平均粒徑爲大之5〇nm〜25 Onm之故，螢光體的亮度上升 之力 方面，如0 7所不，散亂係未變大之故，可使電流 量增加6 %。 接著’作爲波長變換材料而使用平均粒徑2〇螢光體 之平均粒徑200nm〜500nm之Sr3Si05: Eu螢光體，與前 述太陽能電池模組同樣地製作，測定其電流量。在本發明 中’作爲波長變換材料而使用激發帶之適合的螢光體，因 更加使用光變換效率高的波長變換材料之故，太陽能電池 模組的電流量大，比較於未使用波長變換材料之情況，電 流量增加4%。如螢光體的平均粒徑2〇〇nm〜500nm地更 加變大之故’亮度係提昇，但如圖7所示，散亂亦增加之 故’增加的電流量係成爲4 %程度。 接著’作爲波長變換材料而使用平均粒徑400nm〜1 之SrgSiO5: Eu螢光體’與前述太陽能電池模組同樣 地製作’測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 的波長變換材料之故’太陽能電池模組的電流量大，比較 於未使用波長變換材料之情況，電流量增加4 %。如螢光 體的平均粒徑400nm〜lym地更加變大之故，亮度係提昇 -22- 201139615 ’但如圖7所示，散亂亦增加之故，增加的電流量係成爲 4 %程度。 接著’作爲波長變換材料而使用平均粒徑0.8 /z m〜2 以m之SrsSiO5 : Eu螢光體’與前述太陽能電池模組同樣 地製作’測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 的波長變換材料之故，太陽能電池模組的電流量大，比較 0 於未使用波長變換材料之情況，電流量增加5 %。如螢光 體的平均粒徑0.8 # m〜2 " m地更加變大之故，亮度係提 昇，另外如圖7所示，散亂係轉變爲減少之故，可使電流 量增加5 %。 接著，作爲波長變換材料而使用平均粒徑1 // m〜5 // m之Sr3Si05 : Eu螢光體，與前述太陽能電池模組同樣 地製作，測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 〇 的波長變換材料之故，太陽能電池模組的電流量大，比較 於未使用波長變換材料之情況，電流量增加5 %。如螢光 體的平均粒徑1 # m〜5 地更加變大之故，亮度係提昇 ，另外如圖7所示，散亂係轉變爲減少之故，可使電流量 增加5 %。 接著，作爲波長變換材料而使用平均粒徑3 v m〜20 // m之Sr3Si05 : Eu螢光體，與前述太陽能電池模組同樣 地製作，測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 -23- 201139615 的波長變換材料之故，太陽能電池模組的電流量大，比較 於未使用波長變換材料之情況，電流量增加5 %。如螢光 體的平均粒徑3/zm〜20/zm地更加變大之故，亮度係提昇 ’另外如圖7所示’散亂係轉變爲減少之故，可使電流量 增加5 %。 接著’作爲波長變換材料而使用平均粒徑1 5 // m之 (Ba、Sr)2Si〇4: Eu螢光體’與前述太陽能電池模組同樣 地製作’測定其電流量。在本發明中，作爲波長變換材料 而使用激發帶之適合的螢光體，因更加使用光變換效率高 的波長變換材料之故，太陽能電池模組的電流量大，比較 於未使用波長變換材料之情況，電流量增加2.5 %。另外 ’螢光體之亮度壽命係比較於使用有機金屬錯合物之情況 而提昇。 接著，作爲波長變換材料而使用平均粒徑i〇#m2 CaAlSiN3 : Eu螢光體’與前述太陽能電池模組同樣地製 作’測定其電流量。在本發明中’作爲波長變換材料而使 用激發帶之適合的螢光體，因更加使用光變換效率高的波 長變換材料之故’太陽能電池模組的電流量大，比較於未 使用波長變換材料之情況’電流量增加4 %。另外，蛮光 體之亮度壽命係比較於使用有機金屬錯合物之情況而提昇 <太陽能電池模組之製作2 > 接著’說明使用與上述1另外之前述波長變換材料而 -24 - 201139615 製作太陽能電池模組的例。於透明樹脂（EVA )少量添加 有機過氧化物，交聯助劑及黏著提昇材，以〇· 1重量％之 比例，混合平均粒徑 6 // m 之（Ba、Ca、Sr)MgAl1()017 : Eu 、Μη螢光體，使用加熱至80°C之滾輪硏磨機加以混勻之 後，使用沖壓機而夾持於2片之聚乙烯對苯二甲酸酯間， 製作將厚度〇.5mm之EVA爲主成分之封閉材3。另外， 前述螢光體組成係亦可混合使用1種或複數種之組成。 () 接著，將其封閉材3自然冷卻至室溫，剝下聚乙烯對 苯二甲酸酯薄膜，與前面玻璃2，太陽能電池單元4，後 座5同時，如圖1加以層積，以設定成1 5 〇 °c之真空層壓 裝置加以預備壓著。將預備壓著之層積物，以155 °C之烘 烤器進行3 0分鐘加熱，進行交聯及黏著而製作太陽能電 池面板1。在本發明中，作爲波長變換材料而使用激發帶 之適合的螢光體’因更加使用光變換效率高的波長變換材 料之故’太陽能電池面板的電流量大，比較於未使用波長 Ο 變換材料之情況’電流量增加5 %。另外，螢光體之亮度 壽命係比較於使用有機金屬錯合物之情況而提昇。 接著’作爲波長變換材料而使用平均粒徑 10nm~100nm 之（Ba、Ca、Sr)MgAl1()017: Eu、Μη 螢光體 ’與則述太陽能電池模組同樣地製作，測定其電流量。在 本發明中’作爲波長變換材料而使用激發帶之適合的螢光 體，因更加使用光變換效率高的波長變換材料之故，太陽 能電池模組的電流量大’比較於未使用波長變換材料之情 況’電流量增加 5 % 。螢光體之平均粒徑爲小的 -25- 201139615 10nm〜lOOnrn之故，螢光體的亮度爲低，但散亂亦爲 故，亦可使電流量增加5 %。 接著，作爲波長變換材料而使用平均粒徑5 Onm nm 之（Ba、Ca、Sr)MgAl1()017 : Eu、Μη 螢光體，與 太陽能電池模組同樣地製作，測定其電流量。在本發 ，作爲波長變換材料而使用激發帶之適合的螢光體， 加使用光變換效率高的波長變換材料之故，太陽能電 組的電流量大，比較於未使用波長變換材料之情況， 量增加6 %。 接著，作爲波長變換材料而使用平均粒徑200nm nm 之（Ba、Ca、Sr)MgAl1()017: Eu、Μη 螢光體，與 太陽能電池模組同樣地製作，測定其電流量。在本發 ，作爲波長變換材料而使用激發帶之適合的螢光體， 加使用光變換效率高的波長變換材料之故，太陽能電 組的電流量大，比較於未使用波長變換材料之情況， 量增加 4%。如螢光體的平均粒徑 200nm〜500nm地 變大之故，亮度係提昇，但如圖7所示，散亂亦增加 ，增加的電流量係成爲4 %程度。 接著，作爲波長變換材料而使用平均粒徑400nm. //m 之（Ba、Ca、Sr)MgAl1()017: Eu、Μη 螢光體，與 太陽能電池模組同樣地製作，測定其電流量。在本發 ’作爲波長變換材料而使用激發帶之適合的螢光體， 加使用光變換效率高的波長變換材料之故，太陽能電 組的電流量大’比較於未使用波長變換材料之情況， 低之 〜250 前述 明中 因更 池模 電流 〜500 前述 明中 因更 池模 電流 更加 之故 前述 明中 因更 池模 電流 -26- 201139615 量增加4%。如螢光體的平均粒徑400nm〜1 // m地更加變 大之故，亮度係提昇，但如圖7所示，散亂亦增加之故， 增加的電流量係成爲4 %程度。 接著’作爲波長變換材料而使用平均粒徑〇 . 8 // m〜2 从 m 之（Ba、Ca、Sr)MgAl10O17: Eu、Μη 螢光體，與前述 太陽能電池模組同樣地製作，測定其電流量。在本發明中 ’作爲波長變換材料而使用激發帶之適合的螢光體，因更 〇 加使用光變換效率高的波長變換材料之故，太陽能電池模 組的電流量大’比較於未使用波長變換材料之情況，電流 量增加5%。如螢光體的平均粒徑〇.8/zm~2/zm地更加變 大之故’亮度係提昇’另外如圖7所示，散亂係轉變爲減 少之故’可使電流量增加5 %。 接著’作爲波長變換材料而使用平均粒徑1 # m〜5 //m 之（Ba、Ca、Sr)MgAl1()017: Eu、Μη 螢光體，與前述 太陽能電池模組同樣地製作，測定其電流量。在本發明中 〇 ’作爲波長變換材料而使用激發帶之適合的螢光體，因更 加使用光變換效率高的波長變換材料之故，太陽能電池模 組的電流量大，比較於未使用波長變換材料之情況，電流 量增加5%。如螢光體的平均粒徑地更加變 大之故’亮度係提昇’另外如圖7所示，散亂係轉變爲減 少之故’可使電流量增加5 %。 接著’作爲波長變換材料而使用平均粒徑3 V m〜20 ym 2(Ba、Ca、Sr)MgAl1()〇17: Eu、Μη 螢光體，與前述 太陽能電池模組同樣地製作，測定其電流量。在本發明中 -27- 201139615 ’作爲波長變換材料而使用激發帶之適合的螢光體，因更 加使用光變換效率高的波長變換材料之故，太陽能電池模 組的電流量大，比較於未使用波長變換材料之情況，電流 量增加5 %。如螢光體的平均粒徑3 # m〜20以m地更加變 大之故，亮度係提昇，另外如圖7所示，散亂係轉變爲減 少之故，可使電流量增加5%。 [產業上之利用可能性] 本發明係可使用於薄膜多結晶矽太陽能電池，薄膜化 合物半導體太陽能電池，非晶形矽太陽能電池等之太陽能 電池模組。 【圖式簡單說明】 圖1係混合波長變換材料於封閉材之情況的太陽能電 池模組之模式圖。 圖2係於封閉材與太陽能電池元件之間形成波長變換 層之情況的太陽能電池模組之模式圖。 圖3係混合波長變換材料於反射防止膜之情況的太陽 能電池模組之模式圖。 圖4係於反射防止膜與前面玻璃之間形成波長變換層 之情況的太陽能電池模組之模式圖。 圖5係將太陽能電池模組放入於集光型太陽能電池情 況之集光型太陽光發電裝置之模式圖。 圖6係顯示太陽能電池之發電電力增加分的波長變換 -28- 201139615 材料激發端波長依存性的圖表。 圖7係顯示光散亂強度之粒徑依存性的圖表。 圖8係本發明之波長變換材料的激發光譜及發光光譜 〇 圖9係本發明之其他的波長變換材料的激發光譜及發 光光譜。 圖10係本發明之其他的波長變換材料的激發光譜及 0 發光光譜。 圖11係本發明之其他的波長變換材料的激發光譜及 發光光譜。 圖12係本發明之其他的波長變換材料的激發光譜及 發光光譜。 圖1 3係本發明之波長變換材料的激發光譜及發光光 譜。 圖1 4係顯示本發明之波長變換材料之發光強度的添 〇 加濃度依存性的圖表。 【主要元件符號說明】 2 :前面玻璃 :太陽能電池模組 3 :封閉材 :後座 4 :太陽能電池元件 6 :反射防止膜 7 :波長變換材料 8 :波長變換膜 1 0 :支持框 9 :集光透鏡 11 :基板 29 -BaC03 is a composition in which Ba and Ca are substituted for Ba, and the amount of Ca and Eu is small. Further, the concentration of Eu was 15 mol%, and the concentration of Μη was 3 5 m ο 1 %. After the raw materials were mixed in a dry state, the raw material was filled with aluminum oxide in a tubular furnace at 145 ° C, and the atmosphere was reduced with N 2 -H 2 (2% H 2 concentration) for 3 hours. The obtained fired product is cleaved to obtain the desired (Ba, Ca) MgAl|〇〇i7: Eu, Μη green luminescent phosphor ([Ca] = 2.6 mol%) ° -17-201139615 The excitation spectrum and luminescence spectrum of the light body are shown in Fig. 13. When the excitation spectrum is viewed as 'from 300 nm to 460 nm' in a wide range, the excitation band is enlarged. Thus, the case where the excitation band is wide is due to the addition of Eu. In addition, when looking at the luminescence spectrum, there is a peak of luminescence at 515 nm, and the width of the half 値 is narrow and the light is not sharp. The light emission is caused by the Mn composition, and energy transfer from Eu to Mn occurs. The quantum efficiency in the range of 300 nm to 460 nm of the solar cell is generally lower than the neutron efficiency at 515 nm in green. 'The wavelength conversion is performed by using (Ba, Ca) MgAli〇〇i7: Eu, Μ 萤 phosphor. At that time, the photoelectric conversion efficiency of the solar cell can be improved. In the (Ba, Ca) MgAl10O17: Eu, Μη phosphor, the luminescence peak intensity (515 nm) of the 3 65 nm excitation of the sample in which the Ca concentration was changed was shown in Fig. 14 . (Ba, Ca) MgAl1() 017: The luminescence peak intensity of Eu, Μη phosphor is increased by C a Μ g A1, 〇 Ο , 7 : Eu, Μ 萤 phosphor by the addition of C a . Ca is produced by an extremely small amount of addition of O.Omol%. From Fig. 14, the concentration of Ca is smaller than 7 m ο 1 %, and the relative brightness is more than 1 〇〇. Accordingly, the Ca concentration is larger than 0.01 mol% and smaller than 9 mol%, and more preferably, it is larger than 〇8 mol% and more than 4 mol%. When the Ca concentration was taken as 1 mol%, the relative luminescence peak intensity was increased by 6% compared to BaMgAl1Q017: Eu, Μn phosphor. Further, (Ba, Sr) MgAl1G017: Eu, Μη phosphors were produced to measure the luminescence peak intensity of 365 nm excitation. Sr is produced by adding a very small amount of 0.01 mol% to -18-201139615. From Fig. 14', the Sr concentration is smaller than 9 m ο 1 %, and the relative brightness is more than 1 〇 〇. The range of 'S r concentration is larger than O.Olmol% and smaller than 9mo 1% is more appropriate. It is more desirable that the range of 8 mol% is larger than 4 m〇l% or less. In Fig. 14, the amount of Sr is further increased, and in 16 mol% to 18 mol%, the relative luminance exceeds 1 Torr. Then, using the amount of Sr in this range can also improve the effect. When the Sr concentration was taken as 1 mol%, the relative photoluminescence intensity was increased by 4% compared to BaMgAl1() 017: Eu, Μη phosphor. Further, in the same manner as the production of (Ba, Sr, Ca) MgAl1()〇17: Eu, Μη phosphor, the luminescence peak intensity at 3 65 nm excitation was measured. As shown in Fig. 14, the Ca concentration was fixed at 2.6 mol%, and the relative brightness was evaluated by changing the concentration of Sr. In this case, from Fig. 14, the amount of S r is lower than 8 m ο 1 %, and the relative brightness exceeds 1 〇 〇, and the effect appears. When the concentration of S r is further increased, the concentration of Sr is in the range of 14 mol% to 21 mol%, and the relative brightness of the phase exceeds 100. Further, as shown in Fig. 14, when the Sr concentration was 1 mol%, the relative luminescence peak intensity was increased by 7% compared to BaMgAhoO": Eu, Μn phosphor by setting the Ca concentration to 2.6 mol%. By using (Ba, Sr) MgAl1()〇17: eu, Μη, (Ba, Ca)MgAl10O17: Eu, Μη, and (Ba, Sr, Ca)MgAli〇〇i7: Eu, Mn phosphors When the wavelength conversion material is disposed on the solar cell panel, the photoelectric conversion efficiency of the solar cell can be improved. As described above, the excitation wavelength band of the fluorescent system used in the present invention exists in the range of -19-201139615 above 300 nm and the excitation wavelength exists. In the range of 4 10 to 600 nm' and the quantum efficiency system is higher than 0.7. Accordingly, the power generation efficiency of the solar cell can be improved. Further, the average particle diameter of the phosphor used in the present invention is l〇nm~20 # m. Here, the average particle diameter of the phosphor may be specified as follows. As a method of investigating the average particle diameter of the particles (fluorescent particles), there is a method of measuring by a particle size distribution measuring device' and direct electron microscopy Method of observation, etc. In the case of the case of the submicroscope investigation, the average particle diameter can be calculated as follows. The particle size of the particle is variable (..., 0.8 to 丨2 #m, 1·3 to 1.7" m, 1.8 to 2.2#«1 , ..., 6.8 ~ 7.2 " m, 7.3 ~ 7 · 7 / m, 7.8 ~ 8 · 2 / zm, ..., etc.) of each interval, with class 値 (..., l. 〇 / / m, 1.5 / zm , 2.0/zm.....7.0/zm, 7.5/zm, 8_0//m'...), this is taken as Xi. And, as the degree of each variable observed by an electron microscope is taken as Fi indicates that the average 値a is expressed as follows: A = lxj f χ / Ί. \ } = f but Σ f, = N. The wavelength of the excitation band of the fluorescent system of the present invention is suitable as a wavelength conversion material. As a wavelength conversion material for a solar cell, a superior effect can be obtained. <Production of Solar Cell Module 1> Next, a solar cell module is produced using the wavelength conversion material. A small amount of organic peroxidation is added to a transparent resin (EVA). , cross-linking aid -20- 16 201139615 and adhesive lifting material, mixing the average particle size 〆m of Sr3Si05 : Eu phosphor with a ratio of 1% by weight After mixing with a roller machine heated to 80 ° C, the product was sandwiched between two polyethylene dicarboxylates using a press machine to prepare a material 3 having an EVA having a thickness of 55 mm as a main component. The sealing material 3 is naturally cooled to room temperature, and the polyethylene terephthalate film is peeled off, and simultaneously laminated with the front glass 2 and the solar battery unit 40, 5, as shown in Fig. 1, to be set to 1 50 ° C. The vacuum device is pre-pressed. The laminated laminate was prepared and heated in a 1 5 5 t roaster for 30 minutes to crosslink and adhere to form the solar cell module 1. In the present invention, as a wavelength conversion material, a phosphor suitable for use is used, and since a wavelength conversion material having high light conversion efficiency is further used, the amount of current of the solar cell module is large, compared to the case where no conversion material is used. The amount of current increases by 5%. In addition, the lifetime of the phosphor is improved compared to the case of using an organometallic complex. Next, an Sr3Si〇5: Eu phosphor having an average particle diameter of 1 Onm nm was used as a wavelength conversion material, and the solar cell module was produced as described above, and the amount of current was measured. In the present invention, as a suitable phosphor using an excitation band for wavelength conversion, since the wavelength conversion material of the optical conversion effect is further used, the amount of current of the solar cell module is large, and when the wavelength conversion material is not used, The current flow increased by 5%. The average particle size of the flakes is as small as l〇nm~lOOnm, and the brightness of the phosphor is 'but the dispersion is also low, and the current amount can be increased by 5%. Then 'as the wavelength conversion material, the average particle size is 50nm. The honing pair of benzene blocked olefins, the post-lamination baking energy can be changed with the wavelength of the light ~ 100 The same material rate is higher than the light body is -21 - -250 The SQSiO5: Eu phosphor of 201139615 nm was produced in the same manner as the solar cell module described above. In the present invention, a suitable phosphor for use as a wavelength conversion material is used as a wavelength conversion material having high light conversion efficiency, so that the amount of current of the solar cell module is large, compared to the unused wavelength conversion material. In this case, the amount of current increases by 6%. The average particle size of the phosphor is 5 〇 nm to 25 Onm, and the brightness of the phosphor rises. For example, if the brightness of the phosphor is not increased, the amount of current can be increased by 6 %. Then, as the wavelength conversion material, an Sr3Si05: Eu phosphor having an average particle diameter of 2 〇 phosphor and an average particle diameter of 200 nm to 500 nm was used, and was produced in the same manner as the above-described solar cell module, and the amount of current was measured. In the present invention, a suitable phosphor using an excitation band as a wavelength conversion material uses a wavelength conversion material having a high light conversion efficiency, so that the amount of current of the solar cell module is large, compared to the unused wavelength conversion material. In this case, the amount of current is increased by 4%. When the average particle diameter of the phosphor is from 2 nm to 500 nm, the brightness is increased. However, as shown in Fig. 7, the scattering is also increased. The amount of current increased is about 4%. Then, as the wavelength conversion material, SrgSiO5: Eu phosphors having an average particle diameter of 400 nm to 1 were produced in the same manner as in the above-described solar cell module. In the present invention, a suitable phosphor for use as a wavelength conversion material is used as a wavelength conversion material having high light conversion efficiency, so that the amount of current of the solar cell module is large, compared to the unused wavelength conversion material. In this case, the amount of current is increased by 4%. If the average particle diameter of the phosphor is 400 nm to lym, the brightness is increased by -22-201139615'. However, as shown in Fig. 7, the amount of current is increased to about 4%. Then, SrsSiO5: Eu phosphors having an average particle diameter of 0.8 /z m 2 and m in the same manner as in the above-described solar cell module were used as the wavelength conversion material. In the present invention, a suitable phosphor for use as an excitation band is used as a wavelength conversion material, and since a wavelength conversion material having high light conversion efficiency is further used, the amount of current of the solar cell module is large, and 0 is converted to an unused wavelength. In the case of materials, the amount of current is increased by 5%. If the average particle size of the phosphor is 0.8 # m~2 " m is more enlarged, the brightness is increased, and as shown in Fig. 7, the scattering system is reduced to reduce the current amount by 5%. . Next, an Sr3Si05 : Eu phosphor having an average particle diameter of 1 / m to 5 / m / m was used as a wavelength conversion material, and was produced in the same manner as the above-described solar cell module, and the amount of current was measured. In the present invention, a suitable phosphor for use as an excitation band is used as a wavelength conversion material, and a wavelength conversion material having a high light conversion efficiency is used, so that the amount of current of the solar cell module is large, compared to the unused wavelength conversion. In the case of materials, the amount of current is increased by 5%. If the average particle size of the phosphor is 1 #m~5, the brightness is increased, and as shown in Fig. 7, the scattering system is reduced to reduce the current amount by 5%. Next, an Sr3Si05 : Eu phosphor having an average particle diameter of 3 v m to 20 // m was used as a wavelength conversion material, and was produced in the same manner as the above-described solar cell module, and the amount of current was measured. In the present invention, as a wavelength-converting material, a suitable phosphor of an excitation band is used, and since a wavelength conversion material having a high light conversion efficiency of -23-201139615 is used, the amount of current of the solar cell module is large, compared with In the case of using a wavelength converting material, the amount of current is increased by 5%. If the average particle diameter of the phosphor is 3/zm to 20/zm, the brightness is increased. In addition, as shown in Fig. 7, the scattering is reduced, and the amount of current can be increased by 5%. Then, as the wavelength conversion material, (Ba, Sr) 2 Si 〇 4 : Eu phosphor ′ having an average particle diameter of 1 5 // m was produced in the same manner as the solar cell module described above. In the present invention, as a suitable phosphor for use as a wavelength conversion material, a wavelength conversion material having a high light conversion efficiency is used, and the amount of current of the solar cell module is large, compared to the unused wavelength conversion material. In this case, the amount of current increases by 2.5%. In addition, the brightness life of the phosphor is improved compared to the case of using an organometallic complex. Then, as the wavelength conversion material, the average particle diameter i 〇 #m2 CaAlSiN3 : Eu phosphor ’ was produced in the same manner as the solar cell module described above. In the present invention, 'a suitable phosphor that uses an excitation band as a wavelength conversion material has a larger amount of current for a solar cell module because a wavelength conversion material having a higher light conversion efficiency is used more, compared to an unused wavelength conversion material. In the case of 'the amount of current increased by 4%. In addition, the brightness life of the illuminant is improved compared to the case of using the organometallic complex. <Production of the solar cell module 2 > Next, the use of the above-mentioned other wavelength conversion material is described. -24 - 201139615 An example of making a solar cell module. Adding a small amount of organic peroxide, cross-linking aid and adhesion-promoting material to transparent resin (EVA), mixing (Ba, Ca, Sr) MgAl1() with an average particle size of 6 // m at a ratio of 重量·1% by weight 017 : Eu, Μ 萤 phosphor, mixed with a roller honing machine heated to 80 ° C, and then clamped between two pieces of polyethylene terephthalate using a press machine, the thickness will be 〇. 5mm EVA is the main component of the closure material 3. Further, the phosphor composition may be used in combination of one or more kinds. () Next, the sealing material 3 is naturally cooled to room temperature, and the polyethylene terephthalate film is peeled off, and simultaneously laminated with the front glass 2, the solar battery unit 4, and the rear seat 5, as shown in FIG. The vacuum laminating device set to 1 5 〇 °c was preliminarily pressed. The laminate which was prepared to be pressed was heated at 155 ° C for 30 minutes, and crosslinked and adhered to prepare a solar cell panel 1. In the present invention, a suitable phosphor used as an excitation band for a wavelength conversion material has a larger amount of current in a solar cell panel because it uses a wavelength conversion material having a higher light conversion efficiency, and is larger than an unused wavelength Ο conversion material. In the case of 'the amount of current increased by 5%. In addition, the luminance lifetime of the phosphor is improved compared to the case of using an organometallic complex. Then, as a wavelength conversion material, (Ba, Ca, Sr) MgAl1() 017: Eu, Μη phosphor ’ having an average particle diameter of 10 nm to 100 nm was produced in the same manner as in the solar cell module described above, and the amount of current was measured. In the present invention, a suitable phosphor using an excitation band as a wavelength conversion material has a larger amount of current in a solar cell module than a wavelength conversion material having a high light conversion efficiency, as compared with an unused wavelength conversion material. In the case of 'the amount of current increased by 5%. The average particle size of the phosphor is small -25-201139615 10nm~lOOnrn, the brightness of the phosphor is low, but the scattering is also caused, and the current amount can be increased by 5%. Then, (Ba, Ca, Sr) MgAl1() 017: Eu, Μη phosphor having an average particle diameter of 5 Onm nm was used as a wavelength conversion material, and was produced in the same manner as in the solar cell module, and the amount of current was measured. In the present invention, a suitable phosphor for use as an excitation band is used as a wavelength conversion material, and a wavelength conversion material having high light conversion efficiency is used. Therefore, the amount of current in the solar power unit is large, compared to the case where the wavelength conversion material is not used. The amount increased by 6%. Next, a (Ba, Ca, Sr) MgAl1() 017: Eu, Μη phosphor having an average particle diameter of 200 nm nm was used as a wavelength conversion material, and was produced in the same manner as in the solar cell module, and the amount of current was measured. In the present invention, a suitable phosphor for use as an excitation band is used as a wavelength conversion material, and a wavelength conversion material having high light conversion efficiency is used. Therefore, the amount of current in the solar power unit is large, compared to the case where the wavelength conversion material is not used. The amount increased by 4%. If the average particle diameter of the phosphor is as large as 200 nm to 500 nm, the brightness is increased. However, as shown in Fig. 7, the scattering is also increased, and the amount of current increased is about 4%. Then, (Ba, Ca, Sr) MgAl1() 017: Eu, Μη phosphors having an average particle diameter of 400 nm. //m were used as the wavelength conversion material, and were produced in the same manner as in the solar cell module, and the amount of current was measured. In the present invention, a suitable phosphor using an excitation band as a wavelength conversion material and a wavelength conversion material having a high light conversion efficiency are used, and the amount of current in the solar power unit is larger than that in the case where the wavelength conversion material is not used. Low ~250 The above-mentioned Mingzhong due to more pool mode current ~500 The above-mentioned Mingzhong due to more pool mode current is more due to the increase in the current pool mode current -26- 201139615 by 4%. If the average particle diameter of the phosphor is 400 nm to 1 // m, the brightness is increased. However, as shown in Fig. 7, the scattering is also increased, and the amount of current increased is about 4%. Next, 'the average particle diameter of 波长. 8 // m 2 is used as the wavelength conversion material. (Ba, Ca, Sr) MgAl10O17: Eu, Μη phosphor, produced in the same manner as the solar cell module described above, and measured. Electricity flow. In the present invention, 'a suitable phosphor that uses an excitation band as a wavelength conversion material has a larger amount of current for a solar cell module than a wavelength conversion material having a high light conversion efficiency, compared to an unused wavelength. In the case of changing materials, the amount of current is increased by 5%. If the average particle size of the phosphor is 〇.8/zm~2/zm, the brightness is increased. In addition, as shown in Fig. 7, the scattering system is reduced to reduce the current amount. %. Then, as a wavelength conversion material, a (Ba, Ca, Sr) MgAl1() 017: Eu, Μη phosphor having an average particle diameter of 1 #m to 5 //m was used, and was produced in the same manner as the solar cell module described above. The amount of current. In the present invention, a suitable phosphor using an excitation band as a wavelength conversion material uses a wavelength conversion material having a high light conversion efficiency, so that the amount of current of the solar cell module is large, compared to the unused wavelength conversion. In the case of materials, the amount of current increases by 5%. If the average particle size of the phosphor is further increased, the "brightness enhancement" is as shown in Fig. 7, and the scattering is reduced to reduce the current amount by 5%. Then, as the wavelength conversion material, an average particle diameter of 3 V m to 20 μm 2 (Ba, Ca, Sr) MgAl1 () 〇 17: Eu, Μ 萤 phosphor was used, and it was produced in the same manner as the above-described solar cell module, and the measurement was carried out. Electricity flow. In the present invention, -27-201139615 'The phosphor used as the wavelength conversion material and the excitation band is used, and the wavelength conversion material having high light conversion efficiency is further used, so that the amount of current of the solar cell module is large, compared with In the case of using a wavelength converting material, the amount of current is increased by 5%. If the average particle diameter of the phosphor 3 3 m to 20 is further increased by m, the brightness is increased, and as shown in Fig. 7, the scattering is reduced to a decrease, and the amount of current can be increased by 5%. [Industrial Applicability] The present invention can be applied to a solar cell module such as a thin film polycrystalline germanium solar cell, a thin film compound semiconductor solar cell, or an amorphous germanium solar cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a solar battery module in which a wavelength conversion material is mixed in a closed material. Fig. 2 is a schematic view showing a solar battery module in a case where a wavelength conversion layer is formed between a sealing material and a solar cell element. Fig. 3 is a schematic view showing a solar battery module in which a wavelength conversion material is mixed with a reflection preventing film. Fig. 4 is a schematic view showing a solar battery module in a case where a wavelength conversion layer is formed between the anti-reflection film and the front glass. Fig. 5 is a schematic view showing a concentrating solar power generation device in which a solar battery module is placed in a concentrating solar battery. Fig. 6 is a graph showing the wavelength conversion of the power generation power increase of the solar cell -28-201139615. Fig. 7 is a graph showing the particle size dependence of the light scattering intensity. Fig. 8 is an excitation spectrum and an emission spectrum of the wavelength conversion material of the present invention. Fig. 9 is an excitation spectrum and a luminescence spectrum of another wavelength conversion material of the present invention. Fig. 10 is an excitation spectrum and a zero luminescence spectrum of another wavelength conversion material of the present invention. Fig. 11 is an excitation spectrum and an emission spectrum of another wavelength converting material of the present invention. Fig. 12 is an excitation spectrum and an emission spectrum of another wavelength conversion material of the present invention. Fig. 13 is an excitation spectrum and a luminescence spectrum of the wavelength conversion material of the present invention. Fig. 14 is a graph showing the dependence of the luminescence intensity of the wavelength conversion material of the present invention on the concentration dependence. [Main component symbol description] 2: Front glass: Solar battery module 3: Closing material: Rear seat 4: Solar battery element 6: Anti-reflection film 7: Wavelength conversion material 8: Wavelength conversion film 1 0: Support frame 9: Set Optical lens 11: substrate 29 -