201001738 .* 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種製造光電元件（photovoltaic device) 的方法，以及執行該方法的裝置’並且涉及藉此所製造 出的光電元件。 【先前技術】 由於污染的考置以及能量消耗的增加，光電元件（亦 稱之為太陽能電池）已大幅引起關注。光電元件（太陽 能電池）能夠由照射至光電元件（太陽能電池）的太陽 光而產生電能。就照射至太陽能電池之一定量的光而 吕，產生的能量愈多，則太陽能電池的效率愈佳。因此， 一般係以增加光電元件之效率為目的。 亦可稱之為射極和基極。藉由 接點，電荷载子會被帶離開， 太陽能電池之電性損耗來源 太陽能電池包括至少二個具有不同類型之導電性的半 導體區域’以形成-半導體單元。大多數的太陽能電池 包括-由矽所製成的半導體單元，而其具有一 η型摻雜 區以及- Ρ型摻雜區。在具有η型導電性之η型摻雜區， 以及具有ρ型導電性之ρ型摻雜區的介面處，係形成有 半導體接面（junction)，且在此接面之處’藉由照射光 所產生的正負電荷載子係分開。相鄰於”接面的區域 藉由連接至射極與基極的金屬 開，因而可產生電能。 之一為在半導體材料之表 201001738 面與介面處（例如晶界）之電荷的再結合 (re-combination ) ° 為了增進太陽能電池的效率，習知技藝係已知藉由降 低電荷載子在半導體單元之表面處再結合的可能^。因 此，所謂的鈍化層係配置在半導體單元之表面處。此種 鈍化層可以由非晶矽、氫化（hydr〇genated )氮化矽或是 氫化氧化矽。特別的是，氳成分扮演重要的角色，因為 氫會降低自由矽鍵結的數目，因而使得再結合的位置數 量減少。因此，若使用多晶矽或是複晶矽時，氫係有利 於降低在半導體材料（如：矽）内部之再結合位置數量。 多晶矽或是複晶矽之晶界亦作為再結合位置，而氳亦可 降低該處之自由矽鍵結的數量。再者，氫亦可減少金屬 雜質（亦提供再結合位置）之有害效應。 太陽能電池之低效率的進一步原因是照射在太陽能電 池表面或是相應半導體單元之光的反射。為了要減少照 射光之反射，已知在光所照射之太陽能電池的表面上提 供抗反射塗層。此種抗反射塗層可以藉由單一或複數個 薄透明層而形成。且此種抗反射塗層可以由氫化氮化矽 (亦可用作為鈍化層）所形成。因此，氫化氮化矽已廣 泛用作為太陽能電池之鈍化層以及抗反射塗層。 在使半導體單元塗覆有鈍化層或是抗反射塗層之前， 係藉由蝕刻步驟以清潔半導體單元，藉以移除例如形成 在矽半導體單元上之例如為二氧化矽的污染，並且在半 導體單兀以及鈍化層（或抗反射塗層）之間產生一清楚 201001738 的介面。再者，蝕刻可以用於對半導體單元的表面進行 結構化，藉以進一步降低反射損耗。在蝕刻之後，半導 體單元則經過清洗（dnse)以及乾燥，以移除所有的韻 刻劑。201001738 .* SUMMARY OF INVENTION Technical Field The present invention relates to a method of manufacturing a photovoltaic device, and a device for performing the same, and to a photovoltaic element manufactured thereby. [Prior Art] Photoelectric elements (also referred to as solar cells) have attracted a great deal of attention due to the contamination test and the increase in energy consumption. The photovoltaic element (solar cell) can generate electric energy from sunlight that is irradiated to the photovoltaic element (solar cell). In terms of the amount of light that is irradiated to one of the solar cells, the more energy is generated, the better the efficiency of the solar cell. Therefore, it is generally intended to increase the efficiency of the photovoltaic element. It can also be called the emitter and the base. By means of the contacts, the charge carriers are carried away, the source of electrical loss of the solar cell. The solar cell comprises at least two semiconductor regions having different types of conductivity to form a semiconductor unit. Most solar cells include a semiconductor unit made of tantalum having an n-type doped region and a -doped doped region. At the interface of the n-type doped region having n-type conductivity and the p-type doped region having p-type conductivity, a semiconductor junction is formed, and at the junction, 'by illumination The positive and negative charge carriers generated by light are separated. The region adjacent to the junction is electrically connected by the metal connected to the emitter and the base. One of them is the recombination of the charge at the surface of the semiconductor material 2010010738 and the interface (eg, grain boundary) ( Re-combination) ° In order to improve the efficiency of solar cells, conventional techniques are known to reduce the possibility of recombination of charge carriers at the surface of a semiconductor unit. Therefore, a so-called passivation layer is disposed at the surface of the semiconductor unit. Such a passivation layer may be made of amorphous germanium, hydrarged tantalum nitride or hydrogenated ruthenium oxide. In particular, the ruthenium component plays an important role because hydrogen reduces the number of free ruthenium bonds, thus The number of recombined positions is reduced. Therefore, if polycrystalline germanium or polycrystalline germanium is used, the hydrogen system is advantageous for reducing the number of recombination sites inside the semiconductor material (eg, germanium). The grain boundary of polycrystalline germanium or polycrystalline germanium is also By combining the position, the crucible can also reduce the number of free enthalpy bonds there. Further, hydrogen can also reduce the deleterious effects of metallic impurities (also providing recombination sites). A further cause of the inefficiency of solar cells is the reflection of light that illuminates the surface of the solar cell or the corresponding semiconductor unit. In order to reduce the reflection of the illuminating light, it is known to provide an anti-reflective coating on the surface of the solar cell to which the light is illuminated. The anti-reflective coating can be formed by a single or a plurality of thin transparent layers, and the anti-reflective coating can be formed by hydrogenated hafnium nitride (which can also be used as a passivation layer). Therefore, hydrogenated hafnium nitride has been widely used. Used as a passivation layer of a solar cell and an anti-reflection coating. Before the semiconductor unit is coated with a passivation layer or an anti-reflection coating, the semiconductor unit is cleaned by an etching step, thereby removing, for example, formed on the germanium semiconductor unit. For example, it is contamination of cerium oxide, and a clear interface of 201001738 is produced between the semiconductor unit and the passivation layer (or anti-reflective coating). Further, etching can be used to structure the surface of the semiconductor unit, whereby Further reducing the reflection loss. After etching, the semiconductor unit is cleaned (dnse) and dried to remove Some Yun etchant.
上述針對半導體單元之表面而藉由姓刻、清洗、乾燥 及/或其他方法之此種處理係例如描述於 UOf，727,578 以及 US5，川，837 中。獻 US US 4,705,760係描述一種製造半導體元件之方法，其 中在沉積鈍化層之前’係以氟化氨_氟化氫之水溶液來處 理半導體的表面，並在無氧但含有氮的周圍環境 (atmosphere)中’於25°c〜2〇〇t之間以電漿處理半導 體的表面。基於此處理，顯示出由該半導體元件所形成 的光檢器（photo detector)之效能特性增加。然而，電 漿處理係導致高付出。 在上述文獻中所描述之其他半導體晶圓表面的處理及 乾燥方法係包括：利用水性流體（aque〇usfluid)以清洗 表面，並且藉由所謂的有機乾燥溶劑來移除水性流體。 然而，此方法包括基於臭氧處理而氧化該表面，藉以移 除有機乾燥溶劑’而此亦相當費力的。 根據習知技藝，氫化氮化矽SiN:H的鈍化層可以在上 述半導體表面之清潔後而沉積，其係藉由電漿增強化學 氣相沉積（PECVD)、低壓化學氣相沉積（LpcvD)及 常壓化學氣相沉積（APCVD)，並使用矽烷或二氯矽烷及 氣作為反應性虱體而達成（K. Hezel以及R. sch8rner， 201001738Such treatments by surname, cleaning, drying and/or other methods for the surface of the semiconductor unit are described, for example, in UOf, 727, 578 and US 5, Sichuan, 837. US US 4,705,760 describes a method of fabricating a semiconductor device in which the surface of the semiconductor is treated with an aqueous solution of ammonium fluoride-hydrogen fluoride prior to deposition of the passivation layer and in an oxygen-free but nitrogen-containing atmosphere. The surface of the semiconductor is treated with plasma between 25 ° c and 2 〇〇 t. Based on this processing, it is shown that the performance characteristics of the photo detector formed by the semiconductor element are increased. However, plasma processing results in high pay. The processing and drying methods of other semiconductor wafer surfaces described in the above documents include: using an aqueous fluid to clean the surface, and removing the aqueous fluid by a so-called organic drying solvent. However, this method involves oxidizing the surface based on ozone treatment, thereby removing the organic drying solvent, which is also quite laborious. According to the prior art, a passivation layer of yttrium hydrogen hydride nitride SiN:H can be deposited after cleaning of the above semiconductor surface by plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LpcvD), and Atmospheric pressure chemical vapor deposition (APCVD) with decane or dichloromethane and gas as reactive steroids (K. Hezel and R. sch8rner, 201001738)
Interface States and Fixed Charges in MNOS Structures with APCVD and Plasma Silicon Nitride, J. Electrochem. Soc. 13 1 (1984) 1679-1683; T. Pernau, HydrogenInterface States and Fixed Charges in MNOS Structures with APCVD and Plasma Silicon Nitride, J. Electrochem. Soc. 13 1 (1984) 1679-1683; T. Pernau, Hydrogen
Passivation and Silicon Nitride Deposition Using an Integrated LPCVD Process, In Proc. 16th European Photovoltaic Solar Energy Conference (2000) and R.S.R. Hezel, Plasma Si nitride - A promising dielectric to achieve high quality silicon MIS/IL solar cells, J. Appl. Phys. 52 (1981) 3076-3079) » 除了化學氣相沉積製程以外，習知技藝亦已知可以藉 由反應性濺射而產生氫化氮化矽所形成的抗反射塗層或 鈍化層（3.^¥.\^〇11^八.】&〇]<;16，尺.？代11,8.^^(161·，！^· Ruske, SiN:H anti-reflection coatings for c-Si solar cells by large scale inline sputtering, In Proc. 19th EuropeanPassivation and Silicon Nitride Deposition Using an Integrated LPCVD Process, In Proc. 16th European Photovoltaic Solar Energy Conference (2000) and RSR Hezel, Plasma Si nitride - A promising dielectric to achieve high quality silicon MIS/IL solar cells, J. Appl. Phys 52 (1981) 3076-3079) » In addition to the chemical vapor deposition process, it is known in the art to produce an anti-reflective coating or passivation layer formed by yttrium hydrogen hydride by reactive sputtering (3. ^¥.\^〇11^八.]&〇]<;16,foot.?代11,8.^^(161·,!^· Ruske, SiN:H anti-reflection coatings for c-Si Solar cells by large scale inline sputtering, In Proc. 19th European
Photovoltaic Solar Energy Conference, Paris (2004))。氫 化氮化矽之濺射沉積的優點在於，在沉積過程中，氫成 分係較佳受到控制，且可達到鈍化層及/或相鄰半導體之 高氫吸收。然而，由於在矽所形成之半導體以及氫化氮 化石夕（SiN:H )所形成之鈍化層之間的介面出現所謂的起 泡現象（blistering )，則導入鈍化層内以及半導體單元内 的氫含量係受到限制。 【發明内容】 7 201001738 本發明之目的在於進一步增進太陽能電池的效率。特 定的說，本發明之目的在於使鈍化層及/或半導體單元之 氫含量增加。再者，用於達成該些目的之一方法或裝置 應該能夠分別簡易地進行或容易地製造。 本發明之目的可以藉由根據申請專利範圍第丨項所述 之方法、申請專利範圍第26項所述之裝置以及申請專利 範圍第27〜31項所述之光電元件來達成。較佳實施例則 為依附項之標的。 為了要增進光電元件或太陽能電池之效率，本發明係 建議一種製造光電元件的方法，其包括至少一清潔步 驟、至少一乾無步驟以及至少一沉積步驛。 清潔步驟一般係指將污染及不期望之物質由形成光電 元件之半導體單元的表面移除。藉由清潔步驟所清潔的 至少一表面為鈍化層及/或抗反射塗層將要沉積的一表 面’而鈍化層及/或抗反射塗層之目的為降低電荷載子之 再結合。因此，僅有一表面（例如光照射至光電元件的 表面）或是半導體單元之數個或所有表面可以經過清 潔，並在之後塗覆有鈍化層或抗反射塗層。 清潔表面之步驟係藉由蝕刻來執行。「蝕刻」一詞涵蓋 藉由化學及/或物理反應而以原子級（at〇mie scale )移除 表面之物質的每一個方法。可使用不同種類的蝕刻製 程，例如化學乾式蝕刻、化學濕式蝕刻及/或電锻姓刻（一 種由電漿所支持的特別形式之化學乾式钱刻）。 物理蝕刻（如離子束蝕刻）亦使用一蝕刻介質 8 201001738 (―，但是移除物質的方式^ 子或離子的機械式衝擊而移 ：透過原 仆與芬铷碑# *丨&也丨 此外’可使用混合 化子及物理蝕刻的製程，例如電漿蝕刻。 、藉由㈣以清潔表㈣允許產生徹底乾淨的表面，因 為即使疋強力黏附的污染亦期 至嘗被蝕刻介質所溶解。 在本發明之較佳實施例中’餘刻半導體單元（特別曰 时為基礎的半導體單元）係藉由將半導體單元浸入: 釋氫氟酸之蝕刻浴中來進行。 半導體的其他方法。 了使用將氣乾酸施加至 除了餘刻之外，亦可在清潔步驟之過程中進行其他清 潔製程、’，例如=水（特別是去離子水）清洗（rinse)被 韻刻的丰導體皁70。藉由清洗，可將餘刻過程中未分離 的鬆散黏附物質移除。 在藉由清潔步驟製備半導體單元的表面之後’於純化 層及/或抗反射塗層的沉積之前進行乾燥步驟。根據本發 明，乾燥步驟係在實質無氧或是至少為氧耗乏 (〇xygen_depleted)的環境中進行，以避免表面的再氧 化（re-oxidation)。若預防了再氧化的發生，則可以在接 續的沉積步射it到半導料元^效㈣化。特定的 說，如同根據習知技藝之可能發生現象，發現會導入更 多量的氫至鈍化層或抗反射塗層，以及導入半導體單 凡’且特別是多晶或複晶矽中。根據2〇〇5年丨丨月 im Breisgau大學的w. w〇lke之博士論文氣含量的增加 超過-最佳值時’會導致在矽半導體單元與鈍化層之間 201001738 的介面發生起泡現象及形成微氣泡（micr〇sc〇pic 二bble)。然而，在鈍化層及/或抗反射塗層之沉積之前， 若根據本發明之乾燥步驟在無氧環境中進行，則可避免 起泡現象，並可進一步增加氫含量。 相較於US 4,705,760的習知技藝，根據本發明之表面 的製備係相當簡單，且不會受到複雜且昂貴之電漿處理 的影響。 在無氧或減量氧（0Xygen_reduced)的環境中之乾燥步 驟可以採用多種方式進行。一可能性為利用至少一乾燥 惰性氣體（如：氬氣、氦氣、氮氣及/或氖氣）而在氣密 以腔室中沖洗半導體單元。然而’亦可理解到可在無 氧下進行的其他乾燥製程。舉例來說，可降低周圍屋力 j ambient pressure )，藉以使濕氣和液態物質蒸發。壓力 可降低至高真空層級，也就是下降至1〇_7毫巴（mbar) 或至少10·3毫巴。 除此之外，或可選擇地，可以升高溫度以支援蒸發， 且因此支援乾燥。此加熱處理可以在高達5〇〇它，且較 =為间it 70CTC之溫度進行。可藉由抽吸幫浦裝置或真 ，幫浦裝置而使經蒸發的污染自處理腔室排出。再者: 可以藉由如上所述的惰性氣體之氣流而將經蒸發的 導引離開半導體單元。 木 將污染蒸發的另-可行方法為將半導體單元暴露至微 疚0 在進行乾燥步驟時，供應至處理腔室的氣體（如，用 10 201001738 之氣體）可以經過處理以移 選擇地或另外地，此可針對 燥步驟之過程中不時地或連 氣體可經循環。 元之表面上的沉積步驟可藉 賤射）而進行。較佳的，濺 ，意即是，將至少一反應性 的真空腔室中。反應性氣體 產生反應，並形成待沉積在 ’可使用氮氣與氨氣之混合 且使用氬氣作為用於濺射之 作為濺射之靶材物質，即， 。石夕原子與氮形成待沉積在 於氨氣的存在，則會在反應 擴散製程而併入氮化矽層以 氫形成氨之反應（且反之亦 合物來作為反應性氣體混合 ^以及半導體單元中的氫含 於在半導體單元上產生氣流 除或降低殘留的氧含量。可 在處理腔室中的氣體而在乾 續地執行。針對此目的，此 將鈍化層沉積在半導體單 由陰極蒸發製程（亦稱之為 射可以採反應性濺射而執行 氣體導引至進行反應性賤射 與透過賤射所原子化的物質 基板上的成分。針對本發明 物作為反應性氣體混合物， 製程氣體。較佳的，石夕係用 矽原子係由濺射製程所產生 半導體單元上的氮化石夕。由 腔室中產生氫’且氫會藉由 及半導體單元中。由於氮與 然）’則使用氮氣與氨氣之混 物係允許界定出所沉積之^ 量。 另外，反應性氣體混合物的、組《（也就是t氣與氣氣 的比率）不僅是根據沉積層及/或半導體單元中所期望之 風含量而改變，而且該組成亦在沉積過程中改變，藉此， 層的組成係至少在關於氫的含量而在厚度方向上改3變。 由於濺射以及反應性濺射會導致非常均質的層，則層 11 201001738 异度的誤差在整個表面上係小於1.5%。 救射沉積的另 (inline)塗覆裝置中連續地進行。因此，本發明的方法 且特別是沉積步驟可以非常有效地進行。 氣化石夕層，且特別是氫化氮化石夕層，較佳係沉積為純 化層’而其可額外地設計為抗反射塗層。因此，必須設 定鈍化層的厚度，藉此，由於介面與分界層（多重反^ 發生處）之智慧型設計，最終則會導致在半導體單元之 表面的光反射減少。 較佳的，清潔步驟、乾燥步驟及沉積步驟可以進行而 使得在處理步驟過程中或處理步驟之間，半導體單元不 會暴露至含氧周圍環境（atmosphere )。較佳的，清潔步 驟、乾燥步驟及沉積步驟可以接續地進行，其中該些步 驟係連續排列.而相繼進行。 此亦允許用於進行本發明之方法的裝置之有利設計， 其包括用於進行清潔步驟、乾燥步驟及沉積步驟之適當 的處理腔室。這些腔室可以相繼排列，藉此，待處理的 半導體單元可以相繼地移動通過處理腔室，並且進行不 同的處理。 此種裝置亦具有用於不同處理步驟的處理腔室，且該 些處理腔室可以相對其他腔室而關閉，藉此，可以在處 理腔室中建立不同的周圍環境。在此例中，可在處理腔 室之間、農置的入口與出口處提供鎖定單元（1〇ck unit)。 藉由本發明之方法所製造的光電元件具有高氫含量， 12 201001738 而其亦會使得光電元件的效率增加。 【實施方式】 「第1圖」顯示出根據本發明所產生之太陽能電池的 立體視圖。太陽能電池丨包括一半導體單元，且半導體 單兀係藉由具有不同類型之導電性的二半導體層2、3所 形成。舉例來說’ +導體層3具有n型導電性，並且形 成半導體早元2、3之射極。具有ρ型導電性之另一半導 體層2因此代表由半導體層2、3所形成之半導體接面的 基極》 在射極3的該侧，也就是光照射至太陽能電池i之半 導體單元2、3的該侧，係提供有一抗反射塗層或鈍化層 7 » 鈍化層或抗反射塗層7係由氫化氮化妙所製成，並且 包括一或數個分別沉積的層。因此，塗層之厚度係經過 設計’藉此，太陽光之具有一波長範圍的光幾乎不會被 反射。此可以藉由在單一層之間的不同介面處所反射之 部分光束的破壞性干涉或多重反射而達成。因此，可以 降低或幾乎避免該照射光之反射。 在純化層或抗反射塗層7之頂部，係提供有金屬網格 所形成之導電路徑8以及接觸電極4。 在「第1圖」中示出之以太陽能電池1形式存在的光 電元件之背側係覆蓋有一金屬層9以及由另一額外金屬 13 201001738 網格所形成之反電極（counter electrode ) 5。 在太陽能電池1之前側（光側）除了提供金屬網格8 之外，取而代之的，可在表面上配置有近似背側接點之 金屬層9的透明導電層（由氧化銦錫製成）。 在太陽能電池之前側（光側）（即，射極層3的主要表 面）’除了有抗反射塗層7以外，前側可以經過結構化， 藉以形成具有複數個角錐狀突起及/或凹部之丘結構 (hill structure)。此種結構亦可使照射光之反射降低。 鈍化層或抗反射塗層7係根據本發明而產生。由於射 極層3之主要表面係在無氧環境中乾燥，故在清潔步驟 之後，尚含量的氫可以導入由氫化氮化矽所製成的鈍化 層7中，以及由n型摻雜多晶矽所製成的下方射極層3 中。包含在鈍化層中以及鈍化層與射極層3之間的介面 處的氫會導致供照射光所產生之電荷載子進行再結合的 位置減少，而在射極層3或基極層2之多晶矽中所包含 的氫亦然。由於多晶矽之晶界亦會提供電荷载子之再結 合位置，而氫可以降低在晶界處之再結合現象。 由於在乾燥步驟中，環境裡並不存在有氧，因此可能 藉由滅射沉積所執行的沉積步驟而將更多的氫導入鈍化 層7以及射極3與基極2的多晶”。因此，太陽能電 池1之效率可大幅的增加。 本發明之方法可來昭「第9芬1 > ”、、弟2及3圖」而進一步描述，「 2及3圖」係顯示執行本發明之方法的裝置。 「第2圖」顯示用於執行本發 〜々决的裝置10之概 14 201001738 要側視圖 裝置ίο係設計為連續的工作 ^ 作生產線’其具有供設置在 基板承載件11上之其杯9 Λ ΑΛ 土板2〇的傳輪路徑12。 不同的處理腔室13、14、Κ 飞广〆 5、1 6係沿著傳輸路徑12 而並列設置 之真空腔室，藉此允許 圍環境。 處理腔室13-16係設計為氣密 在整個生產製程過程中的無氧周 在處理腔室13、14進行的盆，主、初 項·订的弟一清潔步驟過程中，至少 針對在腔室13中的部分费鞋 τ〜π刀眾私而並不需要無氧周圍環 境，其亦有利於在該些製程中排除氧氣。 本發明方法之清潔步驟係在處理腔室13、14中進行。 清潔步驟包括二部分的步驟：在處理腔室13中的化學濕 式蝕刻，以及在處理腔室14中藉由去離子水清洗基板 20或半導體單元。 因此，處理腔室13包括一酸液儲槽17，其含有稀釋 的氫氟酸，用以在射極層3的主要表面對半導體單元2、 3進行化學濕式餘刻。敍刻的進行係藉由將基板2〇下降 進入酸液儲槽17、18而執行’如「第2圖」之二箭頭所 示。 在對半導體單元2、3所形成的基板20進行蝕刻之後， 基板20係傳送至處理腔室丨4，其中係進行清潔步驟的 第二部分步驟，也就是在去離子水中清洗半導體單元2、 因此，處理腔室14亦包括一儲存去離子水的儲槽19。 15 201001738 基板20再次下降、隹 所示。 降進入去離子水令，如「第2圖」之箭頭 在完成清潔步驟之後，基板 而沿著傳輸路徑12耗5丁 /藉由基板承載件11 仏12移動至下一個處理腔室！5,其中在 此係進行乾燥步驟。 、 根據本發明，乾燥步 — #卜仔在有氧的情況下進 二，因此，用作為處理腔室13_16的真空腔室1316係 實質上不:有氧。為了提供用於乾燥的氣流，處理腔室 15包括-氣體供應器23’且透過氣體供應器。而可將 。 導引至處理腔至15中，並且藉由氣體 供應益23之導引裝置（類似喷嘴，圖中未示）而導引朝 向基板20的表面’以達到沿著基板表面之氣流，或是沿 著射極層3表面的氣流。基於此氣流，則水、濕氣或是 其他物質（例如源自先前清潔步驟之有機物質）可以被 乾燥惰性氣體的氣流所吸收，並且運送至真空腔室（或 處理腔室15)的出口 （圖中未示）。 為了促進黏附至射極表面或是基板表面之污染的移 除’可以增加基板20的溫度或是處理腔室15内部空間 '皿度而藉以增進污染的蒸發。針對此目的，加熱裝 置24 (例如電阻加熱裝置）可以設置在處理腔室15的 内部。 在處理腔室15中進行乾燥之後，基板20係藉由基板 承载件11而運送至處理或真空腔室16，其中係在此進 行純化層或是抗反射塗層的沉積。 16 201001738 處理腔室16亦繪示於「第3圖」中，以說明更多的細 節。 處理腔室或真空腔室10係設計為進行反應性濺射的 裝置。因此，處理腔室16包括用作為陰極的磁控管電極 37。磁控管電極37包括一矽靶材，而矽靶材係藉由在磁 控管電極37前方所產生的電漿34之氬離子的撞擊而原 子化。電漿34的點燃可以藉由分離的微波源（圖中未 示）’或是藉由施加在磁控管電極37以及由基板承載件 11所形成的反電極之射頻電麼（RF電愿）。針對此目的 係提供有功率源3 0。 為了將作為濺射沉積之製程氣體的氬供應至處理腔室 16中，係在處理腔室16配置有一氣體供應器31。 第二氣體供應器32係用於提供反應性濺射之反應氣 體。在本發明之較佳實施例中，由氣體供應器32所供應 之反應氣體為氮氣與氨氣之混合物，藉以提供氮與氫以 沉積在基板20上。氮可以伴隨著在濺射過程中由矽靶材 之原子化所產生的梦原子，而彳以形成氮化_。在處理 腔室16 t氣相中存在的氫係併入氮化矽層，以形成氫化 氮化矽。此外’氫可以擴散進入基板2〇 (即，形成基板 2〇之半導體單元的射極3與基極2)。由於i與氨氣之混 &物的比率則可以設定能夠併入氮化矽以及併入半導 體單凡2、3之多晶石夕的氫含量。因A，可能藉由本發明 之方法Μ定半導體單元2、3之多晶料氫含量，以及 沉積在半導體單元之頂部上而作為純化層之氮化梦層的 17 201001738 氫含量。因此，其可能增加氫含量，並降低電荷載子在 半導體單元中以及鈍化層與半導體單元之間的介面處的 再結合位置。此再次會導致由本發明方法所產生之太陽 能電池的效率增加。 惟本發㈣以實施例而詳細說明如上，但是對於熟習 此技術人員來說，本發明並未限制於該些實施例。針對 說明書中所揭露的所有特徵之不同組合的修飾與修正亦 為可能，或是省略掉實施例之特徵之一也為可能。而其 並未脫離本發明由所时請專利範圍所界定的範嘴。特 定的說，即使單-申請專利範圍僅與其他單_申請專利 範圍有關聯，但本發明包括所有巾請專利範圍的所有可 能之組合。 【圖式簡單說明】 本發明之進-步優點、特徵及特性係由上方之實施例 的描述而變得明顯。本發明係參照圖式而描述之，且圖 式為： 第1圖，根據本發明所製造之太陽能電池之部分的立 體視圖； 第2圖，繪示用於執行本發明的一裝置；以及 第3圖，繪不包含在第2圖中之用於機射沉積的真空 腔室。 【主要元件符號說明】 18 201001738 1 太陽能電池 4 接觸電極 2 半導體層/基極（層）/半導體單元 3 半導體層/射極（層）/半導體單元 5 反電極 7 抗反射塗層/鈍化層 8 導電路徑/金屬網格 9 金屬層 10 裝置 11 承載件 12 傳輸路徑 13,14,15,16 腔室 17,18 酸液儲槽 19 儲槽 20 基板 22 氣體 23 氣體供應器 24 加熱裝置 30 功率源 31 氣體供應器 32 氣體供應器 34 電漿 37 電極 19Photovoltaic Solar Energy Conference, Paris (2004)). An advantage of sputter deposition of tantalum nitride hydride is that the hydrogen component is preferably controlled during deposition and can achieve high hydrogen absorption of the passivation layer and/or adjacent semiconductors. However, due to the so-called blistering of the interface between the semiconductor formed by yttrium and the passivation layer formed by hydrogen hydride nitride (SiN:H), the hydrogen content introduced into the passivation layer and in the semiconductor unit is introduced. It is restricted. SUMMARY OF THE INVENTION 7 201001738 The object of the present invention is to further enhance the efficiency of solar cells. Specifically, it is an object of the present invention to increase the hydrogen content of the passivation layer and/or the semiconductor unit. Furthermore, the method or apparatus for achieving these objectives should be capable of being easily or separately manufactured. The object of the present invention can be attained by the method according to the invention of claim 2, the apparatus described in claim 26, and the photovoltaic element described in claim 27 to 31. The preferred embodiment is the subject matter of the dependent item. In order to increase the efficiency of a photovoltaic element or a solar cell, the present invention proposes a method of fabricating a photovoltaic element comprising at least one cleaning step, at least one dry step, and at least one deposition step. The cleaning step generally refers to the removal of contaminated and undesired materials from the surface of the semiconductor unit forming the photovoltaic element. At least one surface cleaned by the cleaning step is a passivation layer and/or a surface to be deposited by the anti-reflective coating. The purpose of the passivation layer and/or the anti-reflective coating is to reduce the recombination of charge carriers. Thus, only one surface (e.g., light illuminating the surface of the photovoltaic element) or several or all surfaces of the semiconductor unit may be cleaned and subsequently coated with a passivation layer or an anti-reflective coating. The step of cleaning the surface is performed by etching. The term "etching" encompasses every method of removing a substance on a surface by atomic (at 〇mie scale) by chemical and/or physical reaction. Different types of etching processes can be used, such as chemical dry etching, chemical wet etching, and/or electric forging (a special form of chemical dry etching supported by plasma). Physical etching (such as ion beam etching) also uses an etch medium 8 201001738 (", but the way to remove the substance ^ or the mechanical impact of the ions: through the original servant and Finnish monument # * 丨 & also 丨'You can use a process of mixing and physical etching, such as plasma etching. By using (4) to clean the watch (4) allows a thoroughly clean surface to be produced, because even the strong adhesion of the enamel is expected to dissolve in the etched medium. In the preferred embodiment of the present invention, the 'receiving semiconductor unit (in particular, the semiconductor unit based on the time) is performed by immersing the semiconductor unit in an etching bath for hydrofluoric acid. Other methods of semiconductors The gas-drying acid is applied to the cleaning process in addition to the remainder, and other cleaning processes can be performed during the cleaning step, for example, water (especially deionized water) is rinsed by the rhombic conductive soap 70. By cleaning, the loosely adhering substance which is not separated during the process can be removed. After the surface of the semiconductor unit is prepared by the cleaning step, the deposition layer and/or the anti-reflective coating are deposited. The drying step is previously carried out. According to the invention, the drying step is carried out in an environment which is substantially oxygen-free or at least oxygen deficient (de-oxidation) to avoid re-oxidation of the surface. If it occurs, it can be injected into the semi-conducting element in the subsequent deposition step. In particular, it is found that, according to the possible phenomenon of the prior art, it is found that a larger amount of hydrogen is introduced to the passivation layer or the anti-reflective coating. The layer, as well as the introduction of semiconductors, and especially in polycrystalline or polycrystalline germanium. According to the increase in gas content of the doctoral dissertation of w. w〇lke at the University of Bresgau in 2〇〇5 years 'It will cause foaming and microbubbles (micr〇sc〇pic bble) between the interface of the germanium semiconductor unit and the passivation layer 201001738. However, before the deposition of the passivation layer and/or the anti-reflective coating, The drying step according to the present invention is carried out in an oxygen-free environment to avoid foaming and to further increase the hydrogen content. Compared to the prior art of US 4,705,760, the preparation of the surface according to the present invention is relatively simple. And will not be affected by complex and expensive plasma treatment. The drying step in an oxygen-free or reduced oxygen (0Xygen_reduced) environment can be carried out in a variety of ways. One possibility is to utilize at least one dry inert gas (eg argon) Gas, helium, nitrogen and/or helium) to flush the semiconductor unit in a gastight chamber. However, other drying processes that can be carried out without oxygen can be understood. For example, the surrounding force can be reduced. j ambient pressure ), in order to evaporate moisture and liquid substances. The pressure can be reduced to a high vacuum level, ie to 1 〇 7 mbar or at least 10 mbar. Additionally or alternatively, the temperature can be raised to support evaporation and thus support drying. This heat treatment can be carried out at a temperature of up to 5 Torr and at a temperature of between -70 CTC. Evaporated contamination can be expelled from the processing chamber by a pumping device or a true pumping device. Further, the evaporated guide can be guided away from the semiconductor unit by the gas flow of the inert gas as described above. Another possible method for evaporating the contamination of the wood is to expose the semiconductor unit to the micro-zero. When the drying step is performed, the gas supplied to the processing chamber (eg, with 10 201001738 gas) may be treated to selectively or additionally This can be cycled from time to time or even gas during the drying step. The deposition step on the surface of the element can be carried out by means of sputum. Preferably, the splash, i.e., will be at least one reactive vacuum chamber. The reactive gas generates a reaction and forms a target material to be deposited in which a mixture of nitrogen and ammonia can be used and argon is used as a target for sputtering, i.e., . The formation of the atom and nitrogen of the Shixi atom is to be deposited in the presence of ammonia gas, which will be incorporated into the tantalum nitride layer to form ammonia in the reaction diffusion process (and vice versa to be used as a reactive gas mixture and in the semiconductor unit). The hydrogen is contained in the gas stream on the semiconductor unit to remove or reduce the residual oxygen content. The gas in the processing chamber can be continuously performed. For this purpose, the passivation layer is deposited on the semiconductor single cathode evaporation process ( It is also referred to as a component that can be subjected to reactive sputtering to conduct gas guidance to a substrate on which a reactive sputum and a smear are atomized. The present invention is used as a reactive gas mixture, a process gas. Preferably, Shi Xi is using a tantalum atom on a semiconductor unit produced by a sputtering process. The hydrogen is generated from the chamber and hydrogen is used in the semiconductor unit. Nitrogen is used in the semiconductor unit. The mixture with ammonia allows the amount of deposition to be defined. In addition, the group of reactive gas mixtures (that is, the ratio of gas to gas) is not only based on The desired wind content in the layer and/or the semiconductor unit changes, and the composition also changes during the deposition process, whereby the composition of the layer changes at least in the thickness direction with respect to the hydrogen content. And reactive sputtering results in a very homogeneous layer, then the error of the layer 11 201001738 is less than 1.5% over the entire surface. The inline coating apparatus of the salvage deposition is carried out continuously. Therefore, the present invention The method and in particular the deposition step can be carried out very efficiently. The gasification layer, and in particular the hydrogen hydride layer, is preferably deposited as a purification layer' which can additionally be designed as an anti-reflection coating. Therefore, it must be set The thickness of the passivation layer, whereby the intelligent design of the interface and the boundary layer (where multiple reciprocations occur) ultimately leads to a reduction in light reflection at the surface of the semiconductor unit. Preferably, the cleaning step, the drying step and the deposition The steps may be performed such that during or between the processing steps, the semiconductor unit is not exposed to an oxygen-containing atmosphere. Preferably, cleaning The step of drying, the step of drying and the step of depositing may be carried out successively, wherein the steps are successively arranged and successively performed. This also allows an advantageous design of the apparatus for carrying out the method of the invention, which comprises a step of performing a cleaning step, a drying step And appropriate processing chambers for the deposition step. These chambers can be arranged one after the other, whereby the semiconductor units to be processed can be moved successively through the processing chamber and subjected to different processing. Such a device also has different processing steps. Processing chambers, and the processing chambers can be closed relative to other chambers, whereby different environments can be established in the processing chamber. In this case, between processing chambers, farms A locking unit is provided at the inlet and the outlet. The photovoltaic element produced by the method of the present invention has a high hydrogen content, 12 201001738 which also increases the efficiency of the photovoltaic element. [Embodiment] Fig. 1 shows a perspective view of a solar cell produced in accordance with the present invention. The solar cell cartridge includes a semiconductor unit, and the semiconductor unit is formed by two semiconductor layers 2, 3 having different types of conductivity. For example, the + + conductor layer 3 has n-type conductivity and forms the emitter of the semiconductor elements 2 and 3. The further semiconductor layer 2 having p-type conductivity thus represents the base of the semiconductor junction formed by the semiconductor layers 2, 3" on the side of the emitter 3, that is to say the semiconductor unit 2, which is irradiated with light to the solar cell i The side of 3 is provided with an anti-reflective coating or passivation layer 7 » The passivation layer or anti-reflective coating 7 is made of hydrogenated nitriding and comprises one or several separately deposited layers. Therefore, the thickness of the coating is designed so that light having a wavelength range of sunlight is hardly reflected. This can be achieved by destructive or multiple reflections of a portion of the beam reflected at different interfaces between the individual layers. Therefore, the reflection of the illumination light can be reduced or almost avoided. On top of the purification layer or anti-reflective coating 7, a conductive path 8 formed by a metal mesh and a contact electrode 4 are provided. The back side of the photovoltaic element in the form of solar cell 1 shown in "Fig. 1" is covered with a metal layer 9 and a counter electrode 5 formed by another additional metal 13 201001738 grid. Instead of providing the metal mesh 8 on the front side (light side) of the solar cell 1, a transparent conductive layer (made of indium tin oxide) having a metal layer 9 of a back side contact may be disposed on the surface. On the front side (light side) of the solar cell (ie, the main surface of the emitter layer 3) 'in addition to the anti-reflective coating 7, the front side may be structured to form a hill having a plurality of pyramidal protrusions and/or recesses Hill structure. Such a structure can also reduce the reflection of the illuminating light. A passivation layer or anti-reflective coating 7 is produced in accordance with the present invention. Since the main surface of the emitter layer 3 is dried in an oxygen-free environment, after the cleaning step, the still-containing hydrogen can be introduced into the passivation layer 7 made of lanthanum hydrogen hydride, and by the n-type doped polysilicon. Made in the lower emitter layer 3. Hydrogen contained in the passivation layer and at the interface between the passivation layer and the emitter layer 3 causes a decrease in the position at which the charge carriers generated by the illumination light are recombined, and in the emitter layer 3 or the base layer 2 The hydrogen contained in the polycrystalline germanium is also the same. Since the grain boundaries of the polycrystalline germanium also provide recombination sites for charge carriers, hydrogen can reduce recombination at the grain boundaries. Since no oxygen is present in the environment during the drying step, it is possible to introduce more hydrogen into the passivation layer 7 and the polycrystals of the emitter 3 and the base 2 by the deposition step performed by the off-precipitation deposition. The efficiency of the solar cell 1 can be greatly increased. The method of the present invention can be further described in "9th Fen 1 >", "2 and 3", and "2 and 3" shows the execution of the present invention. Method of device. "Fig. 2" shows an overview of the apparatus 10 for performing the present invention. 201001738 The side view apparatus ίο is designed as a continuous operation line which has a cup 9 for being disposed on the substrate carrier 11.传 传 The traverse path of the earth slab 2 。. The different processing chambers 13, 14 and Κ 〆 〆 5, 16 are vacuum chambers juxtaposed along the transport path 12, thereby allowing the environment to be enclosed. The processing chambers 13-16 are designed to be airtight throughout the production process, and the oxygen-free weeks are performed in the processing chambers 13, 14 during the cleaning process, at least in the chamber. The portion of the shoe 13 in the chamber 13 is private and does not require an oxygen-free ambient environment, which is also advantageous in eliminating oxygen in such processes. The cleaning step of the method of the invention is carried out in the processing chambers 13, 14. The cleaning step includes a two-part process: chemical wet etching in the processing chamber 13, and cleaning of the substrate 20 or the semiconductor unit in the processing chamber 14 by deionized water. Accordingly, the processing chamber 13 includes an acid reservoir 17 containing diluted hydrofluoric acid for chemically wetting the semiconductor units 2, 3 on the major surface of the emitter layer 3. The elaboration is performed by lowering the substrate 2 into the acid reservoirs 17, 18 as shown by the arrow "2". After etching the substrate 20 formed by the semiconductor units 2, 3, the substrate 20 is transferred to the processing chamber 4, wherein the second part of the cleaning step is performed, that is, the semiconductor unit 2 is cleaned in deionized water. The processing chamber 14 also includes a reservoir 19 for storing deionized water. 15 201001738 The substrate 20 is lowered again, 隹 shown. Drop into the deionized water, such as the arrow of "Fig. 2" After the cleaning step is completed, the substrate is taken along the transport path 12 by 5 ft / by the substrate carrier 11 仏 12 to the next processing chamber! 5, wherein the drying step is performed here. According to the present invention, the drying step - #卜仔 is advanced in the presence of oxygen, and therefore, the vacuum chamber 1316 used as the processing chamber 13_16 is substantially free of oxygen. In order to provide a gas stream for drying, the processing chamber 15 includes a gas supply 23' and is permeable to the gas supply. And can be. Guided to the processing chamber to 15 and guided by the gas supply benefit 23 (similar to the nozzle, not shown) to the surface of the substrate 20 to achieve airflow along the surface of the substrate, or along The air flow on the surface of the emitter layer 3. Based on this gas flow, water, moisture or other substances (such as organic matter derived from previous cleaning steps) can be absorbed by the gas stream of the dry inert gas and transported to the outlet of the vacuum chamber (or processing chamber 15) ( Not shown in the figure). In order to promote the removal of contamination adhering to the surface of the emitter or the surface of the substrate, the temperature of the substrate 20 or the internal space of the processing chamber 15 can be increased to enhance the evaporation of the contamination. For this purpose, a heating device 24 (e.g., a resistance heating device) may be disposed inside the processing chamber 15. After drying in the processing chamber 15, the substrate 20 is transported by the substrate carrier 11 to a processing or vacuum chamber 16, where a purification layer or deposition of an anti-reflective coating is applied. 16 201001738 Processing chamber 16 is also shown in "Figure 3" to illustrate more details. The processing chamber or vacuum chamber 10 is designed as a device for reactive sputtering. Thus, processing chamber 16 includes a magnetron electrode 37 that serves as a cathode. The magnetron electrode 37 includes a tantalum target which is atomized by the impact of argon ions of the plasma 34 generated in front of the magnetron electrode 37. The ignition of the plasma 34 can be performed by a separate microwave source (not shown) or by a radio frequency applied to the magnetron electrode 37 and the counter electrode formed by the substrate carrier 11 (RF). . A power source 30 is provided for this purpose. In order to supply argon as a sputtering deposition process gas into the processing chamber 16, a gas supply 31 is disposed in the processing chamber 16. The second gas supply 32 is for providing a reactive gas for reactive sputtering. In a preferred embodiment of the invention, the reactant gas supplied by gas supply 32 is a mixture of nitrogen and ammonia to provide nitrogen and hydrogen for deposition on substrate 20. Nitrogen may be accompanied by a dream atom generated by atomization of the ruthenium target during sputtering to form nitridation. The hydrogen present in the gas phase of the treatment chamber 16 t is incorporated into the tantalum nitride layer to form tantalum hydride. Further, hydrogen can diffuse into the substrate 2 (i.e., the emitter 3 and the base 2 of the semiconductor unit forming the substrate 2). The ratio of the mixture of i and ammonia can set the hydrogen content which can be incorporated into the tantalum nitride and incorporated into the semiconductor monolayer 2, 3 polycrystalline. Due to A, it is possible to determine the hydrogen content of the polycrystalline material of the semiconductor units 2, 3 by the method of the present invention, and the hydrogen content of 17 201001738 which is deposited on the top of the semiconductor unit as a nitride layer of the purification layer. Therefore, it is possible to increase the hydrogen content and reduce the recombination position of charge carriers in the semiconductor unit and at the interface between the passivation layer and the semiconductor unit. This again leads to an increase in the efficiency of the solar cell produced by the method of the invention. However, the present invention is described in detail by way of examples, but the present invention is not limited to the embodiments. Modifications and modifications to different combinations of all of the features disclosed in the specification are also possible, or one of the features of the embodiments may be omitted. It does not depart from the scope of the invention as defined by the scope of the patent at the time. In particular, even though the single-application patent scope is only relevant to other patent applications, the invention includes all possible combinations of all patent claims. BRIEF DESCRIPTION OF THE DRAWINGS The advantages, features and characteristics of the present invention are apparent from the description of the embodiments above. The present invention is described with reference to the drawings, and is: FIG. 1 is a perspective view of a portion of a solar cell manufactured according to the present invention; FIG. 2 is a view showing a device for performing the present invention; 3, which depicts the vacuum chamber for machine deposition not included in Figure 2. [Main component symbol description] 18 201001738 1 Solar cell 4 Contact electrode 2 Semiconductor layer/base (layer)/semiconductor unit 3 Semiconductor layer/emitter (layer)/semiconductor unit 5 Counter electrode 7 Anti-reflection coating/passivation layer 8 Conductive path / metal grid 9 Metal layer 10 Device 11 Carrier 12 Transport path 13, 14, 15, 16 Chamber 17, 18 Acid reservoir 19 Reservoir 20 Substrate 22 Gas 23 Gas supply 24 Heating device 30 Power source 31 gas supply 32 gas supply 34 plasma 37 electrode 19