I 1294186 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種光電轉換元件，特別關於一種光電 '轉換效果佳之光電轉換元件。 【先前技術】 隨著地球能源資源逐漸地短缺，開發新能源已成為科 技業以及產業矚目的焦點之一 ’替代性能源產品例如太陽 _ 電池即成為開發的標的之一。太陽電池係為一種利用光伏 特效應(photovoltaic effect)將光能轉換成電能的光電轉換 元件，即利用ρ_η二極體吸收光能量後產生自由電子與電 洞，在ρ-η二極體接面附近的内建電場驅使下，使自由電 子向η塑半導體移動，而自由電洞向Ρ型半導體移動，進 而產生電流，最後經由電極將電流引出形成可供儲存之電 能。 馨 太陽電池一般係以矽為主要材料，依據結晶形式不 :同，又可分為單晶矽太陽電池、、多晶矽太陽電池以及非晶 ;矽太陽電池，其中單晶矽太陽電池之光電轉換效率最好但 成本最高，而非晶矽太陽電池之光電轉換效率最差但成本 最低。請參照圖1所示，習知之一種太陽電池1的基本結 構主要係包含一基板1〇、一 Ρ-η半導體η、一抗反射層 12以及一金屬電極對13。其中，基板10為太陽電池1之 基底，ρ-η半導體11係設置於基板10上，作為將光能轉 換為電能之作用區，另外’習知之太陽電池亦可以Ρ-η半 6 1294186 導體11中之半導體層直接作為基板，抗反射層12則設置 於太陽電池1之入光面，用以降低入射光的反射，而金屬 電極對13係可用於與一外界電路連接。 、 習知之抗反射層12 —般係以例如氮化矽（SiN)等材質 之塗佈於太陽電池1之入光面上，此外，如圖2所示，亦可 於入光面上形成特殊結構14(texturing)例如金字塔型 (pyramid structure)結構，以增加入射光二次入射的機會， 藝來加強抗反射之目的，進而提高光電轉換效率，於此，抗 反射層12係設置於特殊結構14上（圖未顯示）。 然而，為得到如圖2所示之金字塔型結構，在製程上 需搭配上光阻、曝光與蝕刻等黃光製程，因此增加了製程 的複雜度以及製作成本，有鑑於此，如何在增加光電轉換 效率的基礎下’提供一種製程簡單且低製造成本之光電轉 換裳置、光電轉換元件及光電轉換元件之製作方法實為當 今業者的重要課題之一。 '【發明内容】 乂 有鉍於上述課題，本發明之目的為提供一種製程簡單 且製^成本低之光電轉換裝置、光電轉換元件及光電轉換 元件之製作方法。 緣疋為達上述目的，依據本發明之一種光電轉換元 件包3第-半導體層、一第二半導體層以及一多孔洞 層。其中第一半導體層係設置於該第一半導體層上，多孔 洞層係設置於第二半導體層之上，多孔洞層具有相對之一 7 1294186 第一表面與一第二表面，該第一表面係面對第二半導體 層，第二表面係具有複數個孔洞。 為達上述目的，依據本發明之一種光電轉換元件包含 义一第一半導體層、一第二半導體層以及一通孔結構層。其 /中第二半導體層係設置於該第一半導體層上，通孔結構層 係設置於該第二半導體層之上，該通孔結構層具有複數個 通孔。I 1294186 IX. Description of the Invention: [Technical Field] The present invention relates to a photoelectric conversion element, and more particularly to a photoelectric conversion element excellent in photoelectric conversion effect. [Prior Art] With the gradual shortage of the earth's energy resources, the development of new energy sources has become one of the focuses of science and industry and industry. 'Alternative energy products such as the Sun _ battery have become one of the development targets. A solar cell is a photoelectric conversion element that converts light energy into electrical energy by utilizing a photovoltaic effect. That is, the ρ_η diode absorbs light energy to generate free electrons and holes, and the ρ-η diode junction Driven by a nearby built-in electric field, the free electrons move toward the η plastic semiconductor, and the free hole moves toward the Ρ-type semiconductor, which in turn generates a current, and finally draws current through the electrode to form electrical energy for storage. Xin solar cells generally use yttrium as the main material. According to the crystal form, they can be divided into single crystal germanium solar cells, polycrystalline germanium solar cells and amorphous; germanium solar cells, in which the photoelectric conversion efficiency of single crystal germanium solar cells The best but the highest cost, while the amorphous 矽 solar cell has the lowest photoelectric conversion efficiency but the lowest cost. Referring to FIG. 1, a basic structure of a conventional solar cell 1 mainly includes a substrate 1 一, a Ρ-η semiconductor η, an anti-reflection layer 12, and a metal electrode pair 13. Wherein, the substrate 10 is the base of the solar cell 1, and the pn-n semiconductor 11 is disposed on the substrate 10 as an active region for converting light energy into electrical energy, and the conventional solar cell can also be Ρ-η 半6 1294186 conductor 11 The semiconductor layer is directly used as a substrate, and the anti-reflection layer 12 is disposed on the light incident surface of the solar cell 1 to reduce the reflection of incident light, and the metal electrode pair 13 can be used for connection with an external circuit. The conventional anti-reflection layer 12 is generally applied to a light incident surface of the solar cell 1 by a material such as tantalum nitride (SiN), and as shown in FIG. 2, a special surface may be formed on the light incident surface. Structure 14 (texturing), for example, a pyramid structure, to increase the chance of incident secondary light incident, to enhance the anti-reflection purpose, thereby improving the photoelectric conversion efficiency, wherein the anti-reflection layer 12 is disposed in the special structure 14 Up (not shown). However, in order to obtain the pyramid-type structure as shown in FIG. 2, a yellow light process such as photoresist, exposure and etching needs to be matched in the process, thereby increasing the complexity of the process and the manufacturing cost, and in view of this, how to increase the photoelectricity Based on the conversion efficiency, it is one of the important topics of today's industry to provide a photoelectric conversion device, a photoelectric conversion device, and a photoelectric conversion device which are simple in process and low in manufacturing cost. [Explanation] In view of the above problems, an object of the present invention is to provide a photoelectric conversion device, a photoelectric conversion element, and a method for producing a photoelectric conversion element which are simple in process and low in cost. In order to achieve the above object, a photoelectric conversion element package 3 according to the present invention has a first semiconductor layer, a second semiconductor layer and a porous hole layer. The first semiconductor layer is disposed on the first semiconductor layer, and the porous layer is disposed on the second semiconductor layer. The porous layer has a first surface and a second surface opposite to the first surface. The second surface layer faces the second semiconductor layer and has a plurality of holes. To achieve the above object, a photoelectric conversion element according to the present invention comprises a first semiconductor layer, a second semiconductor layer and a via structure layer. The second semiconductor layer is disposed on the first semiconductor layer, and the via structure layer is disposed on the second semiconductor layer, the via structure layer having a plurality of via holes.
為達上述目的，依據本發明之一種光電轉換元件之製 I 作方法包含下列步驟：於一半導體層之上形成一金屬層以 及陽極氧化’處理該金屬層以形成複數個孔洞。 為達上述目的，依據本發明之一種光電轉換元件之製 作方法包含下列步驟：提供一多孔洞層，其之一表面上具 有複數個孔洞、於該多孔洞層之表面上設置一黏著層以及 將該黏著層貼附於一半導體層上，俾使該多孔洞層設置於 該半導體層上。 I 為達上述目的，依據本發明之一種光電轉換裝置包含 久一光電轉換元件以及一電極對。其中光電轉換元件係包含 ;一第一半導體層、一第二半導體層及一多孔洞層，第二半 導體層係設置於第一半導體層上，多孔洞層係設置於第二 半導體層之上，多孔洞層具有相對之一第一表面與一第二 表面，第一表面係面對第二半導體層，第二表面係具有複 數個孔洞；電極對係包含一第一電極及一第二電極分別連 結於第一半導體層與第二半導體層。 為達上述目的，依據本發明之一種光電轉換裝置係包 8 1294186 Π電=以及:電極對。其中先電轉換元件係包 二第-+導體層、-第二半導體層以及一通孔結構層， 第-半導體層係設置於第-半導體層上，通孔結 ^於第二半導體層之上，通孔結構層具有複數個通孔Ί 】對係包含-第—電極及—第二電極分別連結於第一半 導體層與第二半導體層。 纟上所述，㈣據本發明之—種光電轉換裝置、光電 •轉換70件及光電轉換元件之製作方法係將—多孔洞層或 -通孔結構層設置於第二半導體層之上，而多孔洞層^通 孔結構層係分別具有複數孔洞與通孔且可為週期性的排 列’此-多孔層或通孔層為奈米結構，此時折射係數可藉 由孔洞尺寸與間距加以控制，符合等效介質理論使用之聋& ®。藉由折射係數的調整’進而增加了光電轉換之效率。 此外，由於多孔洞層或通孔結構層係可藉由陽極氧化一金 屬層而製成，是以免除了習知製作抗反射結構之例如酸、 •鹼溶液蝕刻或上光阻、曝光與蝕刻等複雜製程，因而簡化 (了製程步驟以及降低了製程成本。 【實施方式】 以下將參照相Μ式’說明依本發明較佳實施例之光 電轉換裝置、光電轉換元件及光電轉換元件之製作方法， 其中相同的元件將以相同的參照符號加以說明。 第一實施例 請參照圖3所示，依據本發明第—實施例之光電轉換 9 1294186 70件2〇係包含—第一半導體層2卜一第二半導體層22以 及夕孔洞層23。 其Φ 第二半導體層22係設置於第一半導體層21上 以形成一接面，舉例來說，第一半導體層21係可為一 pTo achieve the above object, a method of fabricating a photoelectric conversion element according to the present invention comprises the steps of: forming a metal layer over a semiconductor layer and anodizing the metal layer to form a plurality of holes. In order to achieve the above object, a method for fabricating a photoelectric conversion element according to the present invention comprises the steps of: providing a porous layer layer having a plurality of holes on one surface thereof, an adhesive layer on a surface of the porous hole layer, and The adhesive layer is attached to a semiconductor layer, and the porous layer is disposed on the semiconductor layer. In order to achieve the above object, a photoelectric conversion device according to the present invention comprises a photoelectric conversion element and an electrode pair. The photoelectric conversion element comprises: a first semiconductor layer, a second semiconductor layer and a porous hole layer, wherein the second semiconductor layer is disposed on the first semiconductor layer, and the porous hole layer is disposed on the second semiconductor layer, The porous hole layer has a first surface opposite to the second surface, the first surface faces the second semiconductor layer, and the second surface has a plurality of holes; the electrode pair includes a first electrode and a second electrode respectively Connected to the first semiconductor layer and the second semiconductor layer. To achieve the above object, a photoelectric conversion device according to the present invention is a package of 8 1294186 and an electrode pair. The first electrical conversion component is provided with a second +-conductor layer, a second semiconductor layer and a via structure layer. The first semiconductor layer is disposed on the first semiconductor layer, and the via hole is formed on the second semiconductor layer. The via structure layer has a plurality of via holes, wherein the pair includes a first electrode and a second electrode are respectively connected to the first semiconductor layer and the second semiconductor layer. As described above, (4) a method for fabricating a photoelectric conversion device, a photoelectric conversion 70, and a photoelectric conversion element according to the present invention, wherein the porous layer or the via structure layer is disposed on the second semiconductor layer, The porous layer layer has a plurality of holes and through holes and can be periodically arranged. The porous layer or the via layer is a nanostructure. The refractive index can be controlled by the size and spacing of the holes. , in accordance with the theory of equivalent medium used in & The efficiency of photoelectric conversion is further increased by the adjustment of the refractive index. In addition, since the porous hole layer or the via structure layer can be formed by anodizing a metal layer, it is possible to eliminate the conventional anti-reflective structure such as acid, alkali solution etching or photoresist, exposure and etching, etc. The complicated process is simplified, and the process steps are reduced, and the process cost is reduced. [Embodiment] Hereinafter, a photoelectric conversion device, a photoelectric conversion element, and a photoelectric conversion element manufacturing method according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings. The same elements will be described with the same reference symbols. First Embodiment Referring to FIG. 3, the photoelectric conversion according to the first embodiment of the present invention is made up of a first semiconductor layer 2 The second semiconductor layer 22 and the etched layer 23. The Φ second semiconductor layer 22 is disposed on the first semiconductor layer 21 to form a junction. For example, the first semiconductor layer 21 can be a p
型半導# 一 題’而第二半導體層22係為一 η型半導體(如圖3 所當然，第一半導體層21亦可為一 η型半導體，而 、、"導體層22則為一 ρ型半導體’以形成一ρ_η接面， 光伏特效應(photovoltaic effect)作用區。其中ρ型 之摻質例如可以是硼（boron )或鎵（gallium ) 等二價元素，而η型半導體之摻質例如可以是磷 (ph〇Sph〇rus )、砷（arsenic )等五價元素，以擴散法 或離子植入法進行摻雜。 另外，本實施例之多孔洞層23係設置於第二半導體 層22之上，其係具有相對的一第一表面231與一第二表 面232，第一表面231係面對第二半導體層22，第二表面 ⑩232係具有複數個孔洞233。 〈 在本實施例中，多孔洞層23的折射係數舉例來說係 、可為1.86，使其介於第二半導體層22的折射係數與環境 介質（例如空氣或封裝材料例如乙烯基醋酸鹽 (ethylene-vinyl-acetate，EVA等）的折射係數之間’以降低入 射光之反射機會。 另外，如圖4所示，多孔洞層23之複數孔洞233的 至少其中之一係可為一漸減型（deep tapered shape)孔洞’ 更詳細說，該等孔洞233的至少其中之一的孔徑大小係隨 1294186 深度增加而縮減，以此漸減型結構特徵使多孔洞層23之 折射係數具有一梯度(gradient)變化，以加強降低入射光 反射之效果。 ·' 再請參照圖3與4,多孔洞層23係具有一基底234與 •• 一孔洞結構235，孔洞結構235係形成於基底234之上， 其中基底234之材質係包含鋁，孔洞結構235之材質係包 含氧化銘。在本實施例中，該等孔洞233係規則排列使成 一週期性結構例如六角形蜂巢式結構(如圖3所示），當然， _ 此等孔洞233亦可呈不規則排列。多孔洞層23的厚度範 圍係為lOOnm至900nm，其中該等孔洞233的平均深度範 圍係為50nm至300nm，平均孔徑(porediameter)範圍係為 10nm至300nm，且平均單胞尺寸（cellsize)範圍係為50nm 至 lOOOnm。 另外，本實施例之光電轉換元件2()亦可更包含一抗 反射結構（圖未顯示），其係包含複數個凸塊設置於第二半 馨導體層22與多孔洞層23之間，即多孔洞層23係形成於 :抗反射結構上，以增強光電轉換元件2〇之抗反射效果。 ••其中此等凸塊的其中之一係可呈金字塔型、倒金字塔型或 可降低反射之不規則型凸塊。 又，依據本發明第一實施例之光電轉換元件20更可 包含一抗反射層24設置於多孔洞層23之上（如圖5所示）， 亦可形成於上述之抗反射結構上（圖未顯示），其中抗反射 層24之材質的折射係數係小於孔洞結構235之材質的折 射係數，在本實她例中，抗反射層24之材質係可為氧化 1294186 矽。抗反射層24係可以例如但不限定為物理氣相沉積法 (physical vapor deposition)與化學氣相沉積法（physical vapor deposition )等方式堆積於多孔洞層23上，以更加降 低光電轉換元件20之入射光發生反射之機會。 再者，本實施例之光電轉換元件20亦可更包含一透 明導電層設置於多孔洞層23與該第二半導體層22之間（圖 未顯示），其中透明導電層之材質係選自氧化錫、氧化銦 錫、氧化鋁鋅與氧彳t銦鋅至少其中之一。 第二實施例 請參照圖6所示’依據本發明第二實施例之光電轉換 元件30係包含一第一半導體層3卜一第二半導體層32以 及一通孔結構層33。 本實施例之第一半導體層31以及第二半導趙層32之 材質、設置方式與結構特徵係如第一實施例之相同元件所 述，故不再贅述。 唯，本實施例之通孔結構層33係設置於第二半導體 層32之上且具有複數個通孔331，此等通孔331係為規則 性排列，當然並不限於此，此等通孔331亦可為不規則性 排列。如圖6所示，通孔結構層33係可為一六角形蜂巢 式結構所形成的陣列，此等通孔331係垂直於第二半導體 層32，其中通孔結構層33的材質可為氧化鋁，或依實& 需求之不同使用不同之材質。 $ 第二半 料例如 承上所述，通孔結構層33的折射係數係介於 導體32的折射係數與環境介質（例如空氣或封裝材 12 1294186 乙烯基醋酸鹽（ethylene-vinyl-acetate，EVA等）的折射叙 之間’以達到降低入射光反射之目的。 ’、 略 此外，如圖7所示，該等通孔331的至少其中之一係 •可設計為漸減型通孔，即通孔331之孔徑大小係隨深度= 义增加而縮減，而藉此結構特徵使通孔結構層33之折二係 =具有一梯度變化，用以達到加強降低入射光線反射之目 _ 在本實施例中，此等通孔331之平均深度範圍係為 l〇〇nm至900nm ;且此等通孔331的平均單胞尺寸範圍係 為50nm至i000nm，平均孔徑範圍係為1〇1^至3〇〇1^。 另外，在本實施例之光電轉換元件3〇更可包含一抗 反射結構(圖未顯示），其係包含複數個凸塊設置於第二半 導體層32與通孔結構層33之間，其中此等凸塊係可呈金 字塔型或倒金字塔型或可降低反射之不規則型凸塊。又， 光電轉換元件3G亦可更包含—抗反射層34設置於通孔結 _構層33之上（如圖7所示）或上述之抗反射結構上（圖未顯 、示）’其中抗反射層34之材質的折射係數係小於通孔結構 ··層33之材質的折射係數，在本實施例中，抗反射層以之 材質可包括氧化矽，利用抗反射層34以及抗反射結構搭 配通孔結構層33之設置，以更加強光電轉換元件 30之抗 反射效果。 此外，本實施例之光電轉換元件2()亦可更包含一透 明導電層設置於通孔結構層33與該第二半導體層32之間 (圖未顯示），其中透明導電層之材質係可選自氧化錫、氧 13 1294186 化銦錫、氧化鋁鋅與氧化銦鋅至少其中之一。 ^二實施例 ， 再請參照圖8所示，依據本發明第三實施例之光電轉 換元件之製作方法係包含下列步驟·於一半導體層之上形 '成一金屬層S1，以及陽極氧化處理金屬層以形成複數個孔 洞S2。 於步驟S1之前，本實施例之製作方法更包含於另一 _ 半導體上形成此半導體層之步雜SO。 在本實施例中，另一半導體層係可為一 p型半導體或 是一 η型半導體，以下，另一半導體層係以p型半導體為 例。於此，η型半導體係可利用擴散或是離子注入形成於 Ρ型半導體上，藉以形成一 ρ-η接面，提供光電轉換作用 區0 另外，於步驟S1之前，本實施例之製作方法更可包 含於半導體層之上形成一透明導電層，以增加光電轉換元 •件之導電性，其中透明導電層之材質係選自氧化錫、氧化 夂銦錫、氧化鋁鋅與氧化銦鋅至少其中之一。 : 另外，於步驟S1中，於半導體層之上形成金屬層， 於此，金屬層係以蒸鍍或濺鍍方式形成於半導體層之上。 其t，金屬層之材質係包含鋁（例如鋁箔），且其之厚度範 圍係可介於200nm至600nm。 接著，於步驟S1之後而於步驟S2之前，係對金屬層 進行拋光處理。 再者，於步驟S2中，係陽極氧化處理金屬層以形成 1294186 複數個孔洞。於此，係將具有金屬層之半導體層浸至於一 電解液中進行陽極氧化處理，利用控制例如電解液之溫 度、濃度及操作電壓等參數，使在金屬層上形成高密度之 ♦夕孔金屬氧化物孔洞。在本實施例中，銘金屬層於陽極氧 •二化處理後係形成六角形蜂巢式結構，此等孔洞係垂直於鋁 金屬層’於此，此等孔洞之材質係包含氧化鋁，且此等孔 洞之平均深度範圍係為50nm至300nm，平均孔徑範圍係 _ 為10nm至300nm，平均單胞尺寸範圍係為5〇nm至 lOOOnm 〇 另外’在本實施例中，電解液係可包含硫酸、草酸或 磷酸，操作電壓範圍係為10V至200V，操作溫度範圍係 為-5 C 至 50°C。 接著，於步驟S2之後，本實施例之製作方法更可包 含將金屬層浸至一酸性溶液中之步驟S3,以進行擴大此等 孔洞之目的。 議 此外’於步驟S3之後，在本實施例中光電轉換元件 \之製作方法更包含在金屬層之上形成一抗反射層之步驟 、S4’其中抗反射層之材質係包括氧化矽。 差四實施例 請參照圖9所示，依據本發明較佳實施例之一種光電 轉換元件之製作方法係包含下列步驟：提供一多孔洞層， 其之一表面上具有複數個孔洞S1，，於多孔洞層之相對於 此表面之另一表面上設置一黏著層S2，，以及將黏著層貼 附於一半導體層上，俾使多孔洞層設置於半導體層上S3，。 15 1294186 在本實施例，於步驟sr中，多孔洞層係可由一金屬 層陽極氧化處理所形成，如第三實施例所述，金屬層係拋 光處理後浸至一電解液中進行陽極氧化處理，以形成一具 义有複數個孔洞之結構，其中金屬層之厚度範圍係為 200nm '至600nm，且金屬層之材質係包含鋁，於此多孔洞層之材 質係可包含氧化鋁。 另外，在本實施例中，電解液係包含硫酸、草酸或磷 _酸，陽極氧化處理金屬層之電壓範圍係為10V至200V , 操作溫度範圍為至50它，以此條件所形成之該等孔洞 之平均深度範圍係為50nm至30〇nm，平均孔徑範圍係為 l〇nm至300nm，平均單胞尺寸範圍係為5〇nm至1〇〇〇nm。 如第三實施例所述，於步驟S1，之後，本實施例之製 作方法亦更包含將形成多孔洞層之金屬層一酸性溶 液SU，中，以輯擴大孔洞之步l/外層本實施例之製 作方法亦更包含於多孔洞層之上形成一抗反射層sl2，，其 _之材質係包括氮化石夕。 將形成完成之多孔洞層’於具有此等孔洞之表面的相 、對表面設置-黏著層S2，，之後再將黏著層貼附於一半導 體層上，俾使多孔洞層設置於半導體層上幻，，如第三實 施例所述，本實施例之製作方法更包含於另一半導體層上 形成此半導體層之步驟，以及於步驟S3，之前，更包含於 半導體層之上形成-透明導電層，由於本實施例之半導體 層與透明導電層之設置方式與材質係如第三實施例相同 元件所述，故不再贅述。 16 1294186 第五實施例 請參照圖ίο所示，依據本發明第五實施例之光電轉 換裝置2係包含一光電轉換元件20以及一電極對40。 、 光電轉換元件20係包含一第一半導體層21、一第二 --半導體層22及一多孔洞層23。其中光電轉換元件20亦可 更包含一抗反射層24、一抗反射結構以及一透明導電層， 然而，由於本實施例之第一半導體層21、第二半導體層 22、多孔洞層23、抗反射層24、抗反射結構與透明導電 B 層之設置方式、結構特徵與材質特性係如第一實施例之相 同元件所述，故不再贅述。 在本實施例中，第一半導體層21係可形成於一基板 25上抑或利用第一半導體層21作為基板。 電極對40係包含一第一電極41與一第二電極42,其 係分別連結於第一半導體層21與第二半導體層22，當入 射光照射光電轉換元件20時，第一半導體層21與第二半 ϋ 導體層22内係產生電子-電洞對，此電子-電洞對在第一半 :導體層21與第二半導體層22接面所產生之内建電場作用 下而分離，電子與電洞係往相反的方向傳輸而分別由第一 電極41與第二電極42輸出，而為一可供利用之電能。 其中第一電極41與第二電極42係可設置於光電轉換 元件20之相對兩侧，或設計為設置於光電轉換元件20之 一侧0 第六實施例 請參照圖11所示，依據本發明第六實施例之一種光 17 1294186 電轉換裝置3係包含一光電轉換元件3〇以及一電極對％。 光電轉換元件30係包含一第一半導體層31、一第二 半導體層32及一通孔結構層3扣其中光電轉換元件扣亦 •••可更包含一抗反射層34、一抗反射結構以及一透明導電層 ，以更加強光電轉換效率，然而，由於本實施例之第一半導 體層3卜第二半導體層32、通孔結構層33、抗反射層34、 抗反射結構與透明導電層之設置方式、結構特徵與材質特 性係如第二實施例之相同元件所述，故亦不再贅述。 _ 如第六實施例所述，本實施例之光電轉換裝置3的第 一半導體層31係可設置於一基板35之上，當然亦可利用 第一半導體層31作為基板。 電極對50係包含一第一電極51與一第二電極52,其 係分別連結於第一半導體層31與第二半導體層32，如第 五實施例所述，本實施例之第一電極51與第二電極52之 設置方式可於光電轉換元件之相對兩侧或是同一側， φ 以提供光電轉換元件30受入射光之激發後所產生之電子 與電洞的輸出。 \ 綜上所述，因依據本發明之一種光電轉換裝置、光電 轉換元件及光電轉換元件之製作方法係將一多孔洞層或 一通孔結構層設置於第二半導體層之上，而多孔洞層與通 孔結構層係分別具有複數孔洞與通孔且可為週期性的排 列，此一多孔層或通孔層為奈米結構’此時折射係數可藉 由孔洞尺寸與間距加以控制，符合等效介質理論使用之範 圍。藉由折射係數的調整，進而增加了光電轉換之效率。 18 1294186 此外，由於多孔洞層或通孔結構層係可藉由陽極氧化一金 屬層而製成，是以免除了習知製作抗反射結構之例如酸、 鹼溶液蝕刻或上光阻、曝光與蝕刻等複雜製程，因而簡化 ' 了製程步驟以及降低了製程成本。 以上所述僅為舉例性，而非為限制性者。任何未脫離 本發明之精神與範疇，而對其進行之等效修改或變更，均 應包含於後附之申請專利範圍中。 > 【圖式簡單說明】 圖1為一顯示習知之一種太陽電池的立體示意圖； 圖2為一顯示習知之另一種太陽電池的立體示意圖； 圖3至圖5為顯示依據本發明第一實施例之光電轉換 元件的立體示意圖； 圖6與圖7為顯示依據本發明第二實施例之光電轉換 元件的立體示意圖； | 圖8為一顯示依據本發明第三實施例之光電轉換元件 '之製作方法的流程圖； ； 圖9為一顯示依據本發明第四實施例之光電轉換元件 之製作方法的流程圖； 圖10為一顯示依據本發明第五實施例之光電轉換裝 置的立體示意圖；以及 圖11為一顯示依據本發明第六實施例之光電轉換裝 置的立體示意圖。 1294186The second semiconductor layer 22 is an n-type semiconductor (as shown in FIG. 3, the first semiconductor layer 21 may also be an n-type semiconductor, and the " conductor layer 22 is a The p-type semiconductor is formed to form a ρ_η junction, a photovoltaic effect effect region, wherein the p-type dopant may be, for example, a bivalent element such as boron or gallium, and the η-type semiconductor is doped. The material may be, for example, a pentavalent element such as phosphorus (ph〇Sph〇rus) or arsenic, and is doped by a diffusion method or an ion implantation method. Further, the porous layer 23 of the present embodiment is provided in the second semiconductor. Above the layer 22, the first surface 231 and the second surface 232 are opposite to each other. The first surface 231 faces the second semiconductor layer 22, and the second surface 10232 has a plurality of holes 233. In the example, the refractive index of the porous layer 23 is, for example, 1.86, such that it is interposed between the refractive index of the second semiconductor layer 22 and an environmental medium (for example, air or an encapsulating material such as vinyl acetate (ethylene-vinyl-) Between the refractive index of acetate, EVA, etc.) 'To reduce the chance of reflection of incident light. In addition, as shown in FIG. 4, at least one of the plurality of holes 233 of the porous layer 23 may be a deep tapered shape hole. More specifically, the holes The pore size of at least one of 233 is reduced as the depth of 1294186 increases, and the tapered structural feature provides a gradient change in the refractive index of the porous layer 23 to enhance the effect of reducing incident light reflection. Referring to FIGS. 3 and 4, the porous layer 23 has a substrate 234 and a hole structure 235. The hole structure 235 is formed on the substrate 234. The material of the substrate 234 is aluminum, and the material of the hole structure 235. In the present embodiment, the holes 233 are regularly arranged to form a periodic structure such as a hexagonal honeycomb structure (as shown in FIG. 3). Of course, the holes 233 may also be arranged in an irregular arrangement. The thickness of the porous layer 23 ranges from 100 nm to 900 nm, wherein the holes 233 have an average depth ranging from 50 nm to 300 nm, and a pore diameter range of 10 nm to 300 nm, and an average The cell size range is 50 nm to 100 nm. In addition, the photoelectric conversion element 2 () of the embodiment may further include an anti-reflection structure (not shown), which includes a plurality of bumps disposed in the second half. Between the sinusoidal conductor layer 22 and the porous hole layer 23, that is, the porous hole layer 23 is formed on the antireflection structure to enhance the antireflection effect of the photoelectric conversion element 2. • One of these bumps can be pyramidal, inverted pyramid or irregular bumps that reduce reflection. Moreover, the photoelectric conversion element 20 according to the first embodiment of the present invention may further include an anti-reflection layer 24 disposed on the porous layer 23 (as shown in FIG. 5), or may be formed on the anti-reflection structure. Not shown), wherein the refractive index of the material of the anti-reflective layer 24 is smaller than the refractive index of the material of the hole structure 235. In the present example, the material of the anti-reflective layer 24 may be oxidized 1294186 矽. The anti-reflective layer 24 can be deposited on the porous layer 23 by, for example, but not limited to, physical vapor deposition and physical vapor deposition to further reduce the photoelectric conversion element 20 The chance of incident light reflection. Furthermore, the photoelectric conversion element 20 of the present embodiment may further include a transparent conductive layer disposed between the porous hole layer 23 and the second semiconductor layer 22 (not shown), wherein the material of the transparent conductive layer is selected from oxidation. At least one of tin, indium tin oxide, aluminum oxide zinc, and oxonium indium zinc. Second Embodiment Referring to Fig. 6, a photoelectric conversion element 30 according to a second embodiment of the present invention comprises a first semiconductor layer 3, a second semiconductor layer 32, and a via structure layer 33. The materials, arrangement, and structural features of the first semiconductor layer 31 and the second semiconductor layer 32 of the present embodiment are the same as those of the first embodiment, and therefore will not be described again. The via structure layer 33 of the present embodiment is disposed on the second semiconductor layer 32 and has a plurality of through holes 331. The through holes 331 are regularly arranged. Of course, the through holes are not limited thereto. 331 can also be arranged in an irregularity. As shown in FIG. 6, the via structure layer 33 can be an array formed by a hexagonal honeycomb structure, and the through holes 331 are perpendicular to the second semiconductor layer 32. The material of the via structure layer 33 can be oxidized. Use different materials for aluminum, or depending on the requirements of the actual & For the second half of the material, for example, the refractive index of the via structure layer 33 is between the refractive index of the conductor 32 and the environmental medium (for example, air or packaging material 12 1294186 vinyl-acetate (EVA) Between the refractions and the like, in order to reduce the reflection of the incident light. ', Further, as shown in FIG. 7, at least one of the through holes 331 can be designed as a tapered through hole, that is, through The pore size of the hole 331 is reduced as the depth = meaning increases, and the structural feature makes the structure of the through-hole structure layer 33 have a gradient change for enhancing the objective of reducing the reflection of the incident light - in this embodiment The average depth of the through holes 331 ranges from 10 nm to 900 nm; and the average cell size of the through holes 331 ranges from 50 nm to i000 nm, and the average pore size ranges from 1 〇 1 ^ to 3 〇. In addition, the photoelectric conversion element 3 of the present embodiment may further include an anti-reflection structure (not shown) including a plurality of bumps disposed on the second semiconductor layer 32 and the via structure layer 33. Between, where these bumps can be pyramidal An inverted pyramid type or an irregular bump which can reduce reflection. Further, the photoelectric conversion element 3G may further include an anti-reflection layer 34 disposed on the via junction layer 33 (as shown in FIG. 7) or the above In the anti-reflection structure (not shown, shown), wherein the refractive index of the material of the anti-reflection layer 34 is smaller than the refractive index of the material of the through-hole structure layer 33, in the embodiment, the anti-reflection layer is made of a material Including the yttrium oxide, the anti-reflection layer 34 and the anti-reflection structure are matched with the arrangement of the via structure layer 33 to further enhance the anti-reflection effect of the photoelectric conversion element 30. Further, the photoelectric conversion element 2() of the present embodiment may further include A transparent conductive layer is disposed between the via structure layer 33 and the second semiconductor layer 32 (not shown), wherein the transparent conductive layer is made of a material selected from the group consisting of tin oxide, oxygen 13 1294186 indium tin oxide, and aluminum zinc oxide. At least one of indium zinc oxide. ^Two embodiments, and referring to FIG. 8, the manufacturing method of the photoelectric conversion element according to the third embodiment of the present invention comprises the following steps: forming a metal on a semiconductor layer Layer S1, to And anodizing the metal layer to form a plurality of holes S2. Before the step S1, the fabrication method of the embodiment further comprises forming the semiconductor layer on the other semiconductor. In the embodiment, another semiconductor The layer system may be a p-type semiconductor or an n-type semiconductor. Hereinafter, the other semiconductor layer is exemplified by a p-type semiconductor. Here, the n-type semiconductor system may be formed on the germanium-type semiconductor by diffusion or ion implantation. In order to form a ρ-η junction, a photoelectric conversion active region is provided. In addition, before the step S1, the fabrication method of the embodiment may further comprise forming a transparent conductive layer on the semiconductor layer to increase the photoelectric conversion element. Conductivity, wherein the material of the transparent conductive layer is at least one selected from the group consisting of tin oxide, indium tin oxide, aluminum zinc oxide and indium zinc oxide. Further, in step S1, a metal layer is formed on the semiconductor layer, and the metal layer is formed on the semiconductor layer by vapor deposition or sputtering. The material of the metal layer is aluminum (e.g., aluminum foil), and the thickness thereof may range from 200 nm to 600 nm. Next, after the step S1 and before the step S2, the metal layer is subjected to a buffing treatment. Further, in step S2, the metal layer is anodized to form a plurality of holes of 1294186. Herein, a semiconductor layer having a metal layer is immersed in an electrolyte for anodizing, and a high-density metal layer is formed on the metal layer by controlling parameters such as temperature, concentration, and operating voltage of the electrolyte. Oxide holes. In this embodiment, the metal layer is formed into a hexagonal honeycomb structure after the anodic oxygen treatment, and the holes are perpendicular to the aluminum metal layer. The material of the holes is alumina, and The average depth range of the equal pores is 50 nm to 300 nm, the average pore diameter range is 10 nm to 300 nm, and the average unit cell size ranges from 5 〇 nm to 100 Å. In addition, in the present embodiment, the electrolyte system may include sulfuric acid, Oxalic acid or phosphoric acid has an operating voltage range of 10V to 200V and an operating temperature range of -5 C to 50 °C. Then, after the step S2, the manufacturing method of the embodiment may further comprise the step S3 of immersing the metal layer in an acidic solution for the purpose of expanding the holes. Further, after the step S3, in the present embodiment, the method of fabricating the photoelectric conversion element further includes the step of forming an anti-reflection layer on the metal layer, and S4' wherein the material of the anti-reflection layer comprises ruthenium oxide. [Fourth Embodiment] Referring to FIG. 9, a method for fabricating a photoelectric conversion element according to a preferred embodiment of the present invention includes the following steps: providing a porous hole layer having a plurality of holes S1 on one surface thereof, An adhesive layer S2 is disposed on the other surface of the porous layer opposite to the surface, and the adhesive layer is attached to a semiconductor layer, and the porous layer is disposed on the semiconductor layer S3. 15 1294186 In this embodiment, in step sr, the porous hole layer may be formed by anodization treatment of a metal layer. As described in the third embodiment, the metal layer is polished and immersed in an electrolyte for anodizing treatment. To form a structure having a plurality of holes, wherein the thickness of the metal layer ranges from 200 nm ' to 600 nm, and the material of the metal layer comprises aluminum, and the material of the porous layer may comprise aluminum oxide. In addition, in the present embodiment, the electrolyte solution contains sulfuric acid, oxalic acid or phosphorus-acid, and the voltage range of the anodized metal layer is 10V to 200V, and the operating temperature range is up to 50. The average depth of the pores ranges from 50 nm to 30 Å, the average pore size ranges from 10 Å to 300 nm, and the average unit cell size ranges from 5 Å to 1 〇〇〇 nm. As described in the third embodiment, after the step S1, the manufacturing method of the embodiment further includes the step of forming the metal layer of the porous layer into the acidic solution SU, and expanding the hole. The manufacturing method further comprises forming an anti-reflection layer sl2 on the porous hole layer, and the material thereof comprises nitrite. Forming a completed porous layer 'on the surface having the surfaces of the holes, and providing an adhesive layer S2 to the surface, and then attaching the adhesive layer to a semiconductor layer, and then placing the porous layer on the semiconductor layer As described in the third embodiment, the manufacturing method of the embodiment further includes the step of forming the semiconductor layer on another semiconductor layer, and further comprising forming a transparent conductive layer on the semiconductor layer before the step S3. The layer is provided in the manner in which the semiconductor layer and the transparent conductive layer of the present embodiment are disposed in the same manner as the components of the third embodiment, and thus will not be described again. 16 1294186 Fifth Embodiment Referring to the drawings, a photoelectric conversion device 2 according to a fifth embodiment of the present invention includes a photoelectric conversion element 20 and an electrode pair 40. The photoelectric conversion element 20 includes a first semiconductor layer 21, a second semiconductor layer 22, and a porous layer 23. The photoelectric conversion element 20 may further include an anti-reflection layer 24, an anti-reflection structure and a transparent conductive layer. However, due to the first semiconductor layer 21, the second semiconductor layer 22, the porous layer 23, and the anti-reflection layer of the present embodiment, The arrangement, structural features and material properties of the reflective layer 24, the anti-reflective structure and the transparent conductive B layer are as described in the same elements of the first embodiment, and therefore will not be described again. In the present embodiment, the first semiconductor layer 21 can be formed on a substrate 25 or the first semiconductor layer 21 can be used as a substrate. The electrode pair 40 includes a first electrode 41 and a second electrode 42 respectively coupled to the first semiconductor layer 21 and the second semiconductor layer 22. When the incident light illuminates the photoelectric conversion element 20, the first semiconductor layer 21 is An electron-hole pair is formed in the second half of the conductor layer 22, and the electron-hole pair is separated by the built-in electric field generated by the first half: the conductor layer 21 and the second semiconductor layer 22, and the electron It is transmitted in the opposite direction to the hole system and is output by the first electrode 41 and the second electrode 42, respectively, and is an available electric energy. The first electrode 41 and the second electrode 42 may be disposed on opposite sides of the photoelectric conversion element 20 or designed to be disposed on one side of the photoelectric conversion element 20. 6th Embodiment Referring to FIG. 11, according to the present invention A light 17 of the sixth embodiment 1 1294186 The electrical conversion device 3 comprises a photoelectric conversion element 3A and an electrode pair %. The photoelectric conversion element 30 includes a first semiconductor layer 31, a second semiconductor layer 32, and a via structure layer 3, wherein the photoelectric conversion element buckle also includes an anti-reflection layer 34, an anti-reflection structure, and a a transparent conductive layer to further enhance photoelectric conversion efficiency, however, due to the arrangement of the first semiconductor layer 3, the second semiconductor layer 32, the via structure layer 33, the anti-reflection layer 34, the anti-reflection structure and the transparent conductive layer of the present embodiment The manners, structural features, and material characteristics are as described in the same elements of the second embodiment, and therefore will not be described again. As described in the sixth embodiment, the first semiconductor layer 31 of the photoelectric conversion device 3 of the present embodiment can be disposed on a substrate 35, and of course, the first semiconductor layer 31 can be used as a substrate. The electrode pair 50 includes a first electrode 51 and a second electrode 52 respectively connected to the first semiconductor layer 31 and the second semiconductor layer 32. As described in the fifth embodiment, the first electrode 51 of the embodiment The second electrode 52 is disposed on opposite sides or the same side of the photoelectric conversion element, and φ is provided to output the electrons and holes generated by the photoelectric conversion element 30 after being excited by the incident light. In summary, a method for fabricating a photoelectric conversion device, a photoelectric conversion device, and a photoelectric conversion device according to the present invention is to provide a porous layer or a via structure layer on the second semiconductor layer, and the porous layer The through-hole structure layer has a plurality of holes and through holes, respectively, and may be a periodic arrangement. The porous layer or the via layer is a nanostructure. The refractive index can be controlled by the size and spacing of the holes. The range of use of equivalent medium theory. By adjusting the refractive index, the efficiency of photoelectric conversion is further increased. 18 1294186 In addition, since the porous hole layer or the via structure layer can be formed by anodizing a metal layer, it is possible to eliminate the conventional etching of an anti-reflective structure such as acid, alkali solution etching or photoresist, exposure and etching. The complexity of the process, thus simplifying the process steps and reducing the cost of the process. The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the present invention are intended to be included in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing a conventional solar cell; FIG. 2 is a perspective view showing another conventional solar cell; FIG. 3 to FIG. 5 are diagrams showing a first embodiment according to the present invention. 3 is a perspective view showing a photoelectric conversion element according to a second embodiment of the present invention; and FIG. 8 is a perspective view showing a photoelectric conversion element according to a third embodiment of the present invention. FIG. 9 is a flow chart showing a method of fabricating a photoelectric conversion element according to a fourth embodiment of the present invention; FIG. 10 is a perspective view showing a photoelectric conversion device according to a fifth embodiment of the present invention; And Figure 11 is a perspective view showing a photoelectric conversion device according to a sixth embodiment of the present invention. 1294186
元件符號說明： 1 太陽電池 10 基板 11 p-n半導體 12 抗反射層 13 金屬電極對 14 特殊結構 2 光電轉換裝置 20 光電轉換元件 21 第一半導體層 22 第二半導體層 23 多孔洞層 231 第一表面 232 第二表面 233 孔洞 234 基底 235 孔洞結構 24 抗反射層 25 基板 3 光電轉換裝置 30 光電轉換元件 31 第一半導體層 32 第二半導體層 33 通孔結構層 1294186 331 通孔 34 抗反射層 35 基板 \ 40 電極對 • 41 第一電極 42 第二電極 50 電極對 51 第一電極 .52 第二電極 步驟 SO、SI、S2、S3、S4 步驟 SI’、Sir、S12’、S2、S3”Description of the components: 1 solar cell 10 substrate 11 pn semiconductor 12 anti-reflection layer 13 metal electrode pair 14 special structure 2 photoelectric conversion device 20 photoelectric conversion element 21 first semiconductor layer 22 second semiconductor layer 23 porous layer 231 first surface 232 Second surface 233 Hole 234 Substrate 235 Hole structure 24 Anti-reflection layer 25 Substrate 3 Photoelectric conversion device 30 Photoelectric conversion element 31 First semiconductor layer 32 Second semiconductor layer 33 Via structure layer 1294186 331 Via hole 34 Anti-reflection layer 35 Substrate\ 40 electrode pair • 41 first electrode 42 second electrode 50 electrode pair 51 first electrode. 52 second electrode step SO, SI, S2, S3, S4 steps SI', Sir, S12', S2, S3"
21twenty one