201132498 六、發明說明： 【發明所屬之技術領域】 本發明係屬於光伏打模組之領域，且更特定言之，本發 明係屬於併入-聚合物層及-位於一合適薄膜光伏打基板 上之光伏打裝置之薄膜光伏打模組之領域。 【先前技術】 現今使用兩種通用類型的光伏打（太陽能）模組。第一種 類型的光伏打模組採用一半導體晶圓作為一基板且第二種 類型的光伏打模組採用一沈積於一合適基板上之半導體薄 膜。 半導體晶圓類型的光伏打模組通常包括通常用於各種固 態電子裝置（諸如電腦記憶體晶片及電腦處理器）之结晶石夕 晶圓。 薄膜光伏打可併入一合適基板上之一或多個習知半導體 (諸如非晶矽）。不像晶圓應用（其中晶圓係切自一铸旋）， 薄膜光伏打係使用比較簡單的沈積技術（諸如濺鍍塗佈、 物理氣相沈積（PVD)、或化學氣相沈積（CvD))所形成。 薄膜光伏打模組通常併入一乙烯乙酸乙燁酯共聚物 (EVA)層或一聚（乙烯縮丁醛）(PvB)層中以密封及保護下伏 光伏打裝置。該光伏打模組之長期可靠功能（當然）係至關 重要，且因此，聚合物層之穩定性對任何特定光伏打裝置 而言皆係一關鍵因素。 如美國專利公開案第2007/0259998號中詳細描述般，儘 官EVA已廣泛使用於光伏打模組中，然因為聚（乙烯縮丁 147287.doc 201132498 醛）不具有與EVA相同的缺點（諸如乙酸降解），所以非常適 合使用聚（乙稀縮丁酸）。 雖然通常較佳地係利用聚（乙烯縮丁醛），但是已觀察到 在與含銀元件接觸時，聚（乙烯縮丁醛）會變黃。 因此，此項技術中需要的是適合穩定、長期地用於具有 若干金屬元件之光伏打模組之聚（乙烯縮丁醛）組合物。 【發明内容】 本發明提供一種光伏打裝置，其包括金屬及一併入合適 量之1H-苯并三唑之聚（乙烯縮丁醛）層。當將偏壓施加於 該光伏打裝置時，1H_苯并三唑在該金屬/聚（乙烯縮丁醛） 界面上形成一障壁層，其（例如）實際上非預期地消除包括 銀組件之光伏打裝置中之聚（乙烯縮丁醛）的黃化。 【實施方式】 本發明之薄膜光伏打裝置包含一根據本文描述調配而成 之聚(乙烯縮丁醛)層’其為光伏打裝置提供極佳黏著性、 電阻率毪封、可加工性及财久性，且其包含1H-苯并三 口坐° 一本發明之薄膜光伏打模組之實施例大體上以1〇展示於 圆1中。如該圖所$ ’ 一光伏打裝置14係形成於一基底基 板12上，其可為（例如）玻璃或塑料。一保護基板18係使用 一聚（乙烯縮丁醛）層16黏合至光伏打裝置丨4。 如本文所使用，「1H-苯并三唑」係指以下式中所展示 的化合物： 147287.doc 201132498 Ν201132498 VI. Description of the Invention: [Technical Field] The present invention belongs to the field of photovoltaic modules, and more particularly, the invention belongs to an incorporation-polymer layer and is located on a suitable thin film photovoltaic substrate. The field of thin film photovoltaic modules for photovoltaic devices. [Prior Art] Two general-purpose types of photovoltaic (solar) modules are used today. The first type of photovoltaic module uses a semiconductor wafer as a substrate and the second type of photovoltaic module uses a semiconductor film deposited on a suitable substrate. Photovoltaic modules of the semiconductor wafer type typically include crystallographic wafers commonly used in various solid state electronic devices, such as computer memory chips and computer processors. Thin film photovoltaics can be incorporated into one or more conventional semiconductors (such as amorphous germanium) on a suitable substrate. Unlike wafer applications where the wafer is cut from a single spin, thin film photovoltaics use relatively simple deposition techniques such as sputter coating, physical vapor deposition (PVD), or chemical vapor deposition (CvD). ) formed. Thin film photovoltaic modules are typically incorporated into an ethylene vinyl acetate copolymer (EVA) layer or a poly(vinyl butyral) (PvB) layer to seal and protect the underlying photovoltaic device. The long-term reliability of the photovoltaic module (of course) is critical and, therefore, the stability of the polymer layer is a critical factor for any particular photovoltaic device. As described in detail in U.S. Patent Publication No. 2007/0259998, EVA has been widely used in photovoltaic modules, because poly(ethylene butyl 147287.doc 201132498 aldehyde) does not have the same disadvantages as EVA (such as Acetic acid degrads), so it is very suitable to use poly(ethylene succinic acid). Although poly(vinyl butyral) is generally preferred, it has been observed that poly(vinyl butyral) turns yellow when contacted with a silver-containing member. Accordingly, what is needed in the art is a poly(vinyl butyral) composition suitable for stable, long-term use in photovoltaic modules having several metal components. SUMMARY OF THE INVENTION The present invention provides a photovoltaic device comprising a metal and a poly(vinyl butyral) layer incorporating a suitable amount of 1H-benzotriazole. When a bias voltage is applied to the photovoltaic device, 1H_benzotriazole forms a barrier layer on the metal/poly(vinyl butyral) interface, which, for example, virtually unintentionally eliminates the inclusion of silver components. Yellowing of poly(vinyl butyral) in photovoltaic devices. [Embodiment] The thin film photovoltaic device of the present invention comprises a poly(vinyl butyral) layer formulated according to the description herein, which provides excellent adhesion, resistivity, processability and profitability for a photovoltaic device. Long-lasting, and including 1H-benzotriene, an embodiment of a thin film photovoltaic module of the present invention is shown generally in a circle 1 in a circle. A photovoltaic device 14 as shown in the figure is formed on a base substrate 12, which may be, for example, glass or plastic. A protective substrate 18 is bonded to the photovoltaic device 4 using a poly(vinyl butyral) layer 16. As used herein, "1H-benzotriazole" refers to a compound as shown in the following formula: 147287.doc 201132498 Ν
式I 1 Η-笨并二唑可以任何合適的量包含於聚（乙烯縮丁酿） 層中，且在各種實施例中，所含1Η-苯并三。坐之重量百分 比為 0.001至 5%、〇.〇1 至 5%、（^至弓％、1至5%、2至5%， 或 0.1 至 0.4%。 較佳地，1Η-苯并三唑係在經由使丨苯并三。坐與聚（乙 烯縮丁醛）樹脂及任何其他添加劑熔融混合而形成一聚合 物層時包含於該聚（乙烯縮丁醛）中。1Η_苯并三唑亦可以 鹽的形式（例如鈉、鉀，及敍）提供。 1Η-苯并三唑係一種用於銅、銀、鈷、鋁及辞之已知腐 蝕抑制劑《其在商業上可購自PMC精化公司（PMC Specialties Group)，並以c〇brate_99之商標名販售。本發 明之光伏打裝置中適用的其他腐蝕抑制劑包含：ih_苯并 三。坐之衍生物，諸如基孤苯并三唾，5_絲苯并: 坐，及1H-本并二唑之其他烷基衍生物；咪唑及咪唑衍生 物’諸如苯并Μ、5,6_二甲基料W、㈣基笨并味 。坐’及4,5-二氫_出-咪唑之脂肪酸衍生物；噻二唑及嗜二 唾之烧純生物，諸如㈣基笨并㈣，^.二（笨硫基― 乙烧、2,5-雙（正辛基二硫）_u，4_嗔二。坐、2_胺基、4 基、M’4-噻二。坐、2,基鳴啶、2,基苯并十坐；组胺. 組胺酸；及2-胺基嘧啶。 ’ 147287.doc 201132498 其他添加劑 其他添加劑（其可包含於本發明之聚合物層中以改良穩 疋丨生及丨生此）包含金屬純化劑’諸如Irganox MD-1024® (CAS 32687-78-8)及 Naugard XL-1®(CAS 70331-94-1);受 阻胺光穩定劑’諸如Tinuvin i23®(CAS129757-67-l);及 酚系抗氧化劑，諸如Anox 7〇®(22,_硫二伸乙基雙[3_(3,5_ 一-第二丁基-4-經基苯基）丙酸酯]cas 41484-35-9)。 期望上述任何聚合物穩定劑與苯并三唑之組合使聚（乙 烯縮丁醛）在該聚（乙烯縮丁醛）_金屬界面及聚合物内側處 達到進一步穩定性。實驗資料已暗示：添加苯并三唑及 Anox 70至聚（乙埽縮丁酸）調配物中確實進一步降低聚合 物褪色並保濩溥膜太陽能板之結構。在本發明之各種實施 例中，1H-苯并三唑及酚系抗氧化劑係併入一聚（乙烯縮丁 醛）層中，且在一些實施例中，1H_苯并三唑及2,2,_硫二伸 乙基雙[3-(3,5-二-第三丁基_4_羥基苯基）丙酸酯]係併入一 聚（乙烯縮丁醛）層中。 聚（乙烯縮丁醛）層 本發明之薄膜光伏打模組係採用一聚（乙烯縮丁醛）層作 為一層壓黏著劑，其係用於將該光伏打裝置密封於一保護 基板上’藉此形成本發明之光伏打模組。 如热習此項技術者所知（例如，參見美國專利第 2,282,057號及第2,282,〇26號），本發明之聚（乙烯縮丁醛） 可藉由縮醛化方法產生。在一實施例中，可使用聚合物科 學與工藝大全（Encyclopedia of P〇iymei· Scie_ & 147287.doc 201132498The oxime- benzobisazole may be included in the poly(ethylene butyl) layer in any suitable amount, and in various embodiments, contains 1 Η-benzotriene. The weight percentage of sitting is 0.001 to 5%, 〇.〇1 to 5%, (^ to bow%, 1 to 5%, 2 to 5%, or 0.1 to 0.4%. Preferably, 1 Η-benzotriazole It is contained in the poly(vinyl butyral) by melt-mixing the phthalocyanine with a poly(vinyl butyral) resin and any other additives. 1Η_benzotriazole It can also be supplied in the form of a salt (for example, sodium, potassium, and sulphur). 1 Η-benzotriazole is a known corrosion inhibitor for copper, silver, cobalt, aluminum and the words "commercially available from PMC. PMC Specialties Group, sold under the trade name c〇brate_99. Other corrosion inhibitors suitable for use in the photovoltaic device of the present invention include: ih_benzotriene. And three saliva, 5_ silk benzo: sit, and other alkyl derivatives of 1H-benzazole; imidazole and imidazole derivatives such as benzopyrene, 5,6-dimethyl material W, (four) base And taste. Sitting on the 'and 4,5-dihydro-ex-imidazole fatty acid derivatives; thiadiazole and dipyridamole pure organisms, such as (four) base stupid (four), ^. two (stupidyl Ethylene, 2,5-bis(n-octyldisulfide)_u, 4_嗔2. Sit, 2_amino group, 4 base, M'4-thiazide. Sit, 2, ketone, 2, base Benzene; histamine. Histamine; and 2-aminopyrimidine. '147287.doc 201132498 Other additives Other additives (which may be included in the polymer layer of the present invention to improve stability and hygiene) Contains metal purifiers such as Irganox MD-1024® (CAS 32687-78-8) and Naugard XL-1® (CAS 70331-94-1); hindered amine light stabilizers such as Tinuvin i23® (CAS129757-67- l); and phenolic antioxidants, such as Anox 7〇® (22, _ thiodiethyl bis[3_(3,5_--di-butyl-4-phenylphenyl)propionate] cas 41484 -35-9) It is expected that any combination of any of the above polymeric stabilizers with benzotriazole will result in further stability of the poly(vinyl butyral) at the poly(vinyl butyral)-metal interface and the inner side of the polymer. Experimental data has suggested that the addition of benzotriazole and Anox 70 to poly(ethyl acetal) formulations does further reduce polymer fading and preserve the structure of the solar panel. In various embodiments of the invention, 1H- And the triazole and phenolic antioxidants are incorporated into a poly(vinyl butyral) layer, and in some embodiments, 1H_benzotriazole and 2,2,-thiadiethylidene [3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] is incorporated into a poly(vinyl butyral) layer. Poly(vinyl butyral) layer of the present invention The module uses a poly(vinyl butyral) layer as a laminating adhesive for sealing the photovoltaic device to a protective substrate, thereby forming the photovoltaic module of the present invention. The poly(vinyl butyral) of the present invention can be produced by an acetalization process, as is known to those skilled in the art (see, for example, U.S. Patent Nos. 2,282,057 and 2,282, 〇26). In one embodiment, the Encyclopedia of P〇iymei·Scie_ & 147287.doc 201132498 can be used.
Technology)，第三版，第8卷，第381至399頁中B e Wade (2003)之縮醛乙烯（vinyi acetal)聚合物中所描述的溶 劑法。在另一實施例中，可使用其中所描述的水化法。聚 (乙稀縮丁輕）在商業上可以各種形式購自（例如）s〇lutia Inc.，也蘇裡州，聖路易市，如ButvarTM樹脂。 在各種實施例中，聚（乙烯縮丁醛）包括以聚乙烯醇算得 10至35重量百分比（wt.%)的羥基、以聚乙烯醇所算得13至 30 wt·%的羥基或以聚乙烯醇算得15至22 wt %的羥基。聚 合物層樹脂亦可包括少於15 wt.%的殘餘酯基、以聚乙酸 乙烯醋算得 13 wt %、n wt %、9 wt %、7 wt %、$ wt.°/〇，或少於3 wt %的殘餘酯基，剩餘物為縮醛，較佳為 丁醛縮醛，但可視情況地包含微量之其他縮醛基（例如）2_ 乙基己醛基（例如’參見美國專利第5，i37,954號）。 在各種實施例中’聚（乙烯縮丁醛）具有每莫耳至少 30.000、 40,000、50,000、55,〇〇〇 ' 6〇 〇〇〇、65 〇〇〇、 70.000、 120,000、250,000’ 或至少 35〇〇〇〇 克（g/m〇le 或道 爾頓）之分子量。亦可在縮醛化步驟期間加入少量的二醛 或三醛，以將分子量增加至至少35〇,〇〇〇 g/m〇le(例如，參 見美國專利第4,902,464號、第4,874,814號、第4,814,529 唬，及第4,654，179號）。如本文中所使用，術語「分子 量」意謂重量平均分子量。 本發明之聚合物層中可使用多種黏著控制劑，包含乙酸 鈉、乙酸鉀，及鎂鹽。可與本發明之此等實施例一起使用 之鎂鹽包含（但不限於）美國專利第5,728,472號中所揭示 147287.doc 201132498 者，諸如水楊酸鎂、菸鹼酸鎂、二（2_胺基苯甲酸）鎂、二 (3-羥基-2-萘酸）鎂，及雙（2-丁酸乙酯）鎂（化學摘要第 79992-76-0號）。在本發明之各種實施例中，該鎂鹽為雙 (2-丁酸乙酯）鎂。 又 在本發明之聚合物層之各種實施例中，該聚合物層可包 含20至60、25至60、20至80、1〇至7〇，或1〇至1〇〇份之增 塑劑。當然，只要適合用於特定應用，就可以使用其他 量。在一些實施例中，增塑劑具有一少於2〇個、少於Μ 個、少於12個，或少於10個碳原子之烴段。增塑劑的量可 經調整以影響聚（乙烯縮丁醛）層之玻璃轉變溫度（Tg)。一 身又5之，可添加較大量的增塑劑以降低Tg。 爲了形成聚合物層，可將任何合適的增塑劑添加至本發 明之該等聚合物樹财本發明之聚合物層中所使用的增 塑劑其中可包含多元酸酯或多元醇。合適的增塑劑包含 (例如）二乙二醇二_(2_乙基丁酸酯）、三乙二醇二兴2_乙基 己IS日）一乙一醇二庚酸酯 '四乙二醇二庚酸酯、己二 一己基S曰、己二酸二辛基酯、己二酸己基環己基酯、己 一 ®文庚基®曰與壬基酿的混合物、己二酸二異壬基酿、己二 酸庚基壬基酯、癸二酸二丁酯、諸如經油改質之癸二酸醇 S欠之聚。物增塑劑、諸如美國專利第3,84丨，89〇號所揭示之 鱗酸S旨與己二酸@旨的混合物、諸如美國專利第4，144,217號 所揭不之己二酸酯，及以上所述物之混合物與組合物。可 使用之其他增塑劑係由G至C9烷醇及(：4至Cl〇環烷醇製成 的混合己二酸酯（如美國專利第5,013,779號中所揭示般）， 147287.doc 201132498 以及<：6至(：8己—酸酯’諸如己二酸己基酯。在各種實施例 中，所用的增塑劑為己二酸二己基酿及/或三乙二醇二_2_ 乙基己酸s旨。 根據彼等一般技術者已知的方法，聚（乙烯縮丁酸）聚合 物、增塑劑’及任何添加劑可經熱處理並配置成薄片形 式。形成-聚(乙烯縮丁醛)薄片之例示性方法包括藉由迫 使熔融物通過一鑄模(例如’ 一維度大體上大於垂直維度 之開口之鑄模）而擠壓熔融的聚（乙烯縮丁醛）（其包括^ 月曰、增塑劑，及若干添加劑卜形成一聚（乙烯縮丁醛）薄片 之另一例示性方法包括將來自一鑄模之熔融物鑄造成一滾 筒，固化樹脂，並大體上移除呈薄片形式之該固化樹脂。 在各種實施例中，聚合物層可具有（例如）〇1至2 5毫米、 0.2至2.0毫米、〇·25至1_75毫米，及〇.3至1.5毫米之厚度。 本务明之聚（乙烯縮丁酸）層可包含低分子量之環氧樹脂 添加劑。如此項技術中已知（例如，參見美國專利第 5,529,848號及苐5,529,849號），任何合適的環氧樹脂劑皆 可與本發明一起使用。 可將其他添加劑併入聚合物薄片中以提高其在最終產品 中之性能。如此項技術中已知，此等添加劑包含（但不限 於）染料、顏料、穩定劑（例如’紫外線穩定劑）、抗氧化 劑、防阻塞劑、額外紅外線吸收劑、阻燃劑、上述添加劑 之組合及類似物。 典型的紫外線穩定劑包含經取代之2Η-笨并三唑，諸如 彼等由汽巴精化有限公司（Ciba specialty Company)以 147287.doc 201132498Technology), Third Edition, Volume 8, pages 381 to 399, the solvent method described in Bé Wade (2003) vinyi acetal polymer. In another embodiment, the hydration process described therein can be used. Poly (ethylene butyl butyl) is commercially available in various forms, for example, from s〇lutia Inc., also in Suri, Suri, such as ButvarTM resin. In various embodiments, the poly(vinyl butyral) comprises from 10 to 35 weight percent (wt.%) of hydroxyl groups, from polyvinyl alcohol, from 13 to 30 wt% of hydroxyl groups or from polyethylene. The alcohol has 15 to 22 wt% of hydroxyl groups. The polymer layer resin may also include less than 15 wt.% of residual ester groups, 13 wt% of polyvinyl acetate, n wt %, 9 wt %, 7 wt %, $ wt. ° /〇, or less 3 wt % of residual ester groups, the remainder being an acetal, preferably butyraldehyde acetal, but optionally containing minor amounts of other acetal groups (for example) 2-ethylhexanal (eg 'see US Pat. No. 5 , i37, 954). In various embodiments, 'poly(vinyl butyral) has at least 30.000, 40,000, 50,000, 55, 〇〇〇'6〇〇〇〇, 65 〇〇〇, 70.000, 120,000, 250,000' or at least 35 per mole. The molecular weight of gram (g/m〇le or dalton). A small amount of dialdehyde or trialdehyde may also be added during the acetalization step to increase the molecular weight to at least 35 Å, 〇〇〇g/m〇le (see, for example, U.S. Patent Nos. 4,902,464, 4,874,814, 4,814,529唬, and No. 4, 654, 179). As used herein, the term "molecular weight" means a weight average molecular weight. A variety of adhesion control agents can be used in the polymer layer of the present invention, including sodium acetate, potassium acetate, and magnesium salts. Magnesium salts which may be used with such embodiments of the invention include, but are not limited to, those disclosed in U.S. Patent No. 5,728,472, the disclosure of which is incorporated herein by reference. Magnesium benzoate, magnesium bis(3-hydroxy-2-naphthoate), and magnesium bis(2-butyrate) (Chemical Abstract No. 79992-76-0). In various embodiments of the invention, the magnesium salt is magnesium bis(2-butyrate). In still various embodiments of the polymer layer of the present invention, the polymer layer may comprise from 20 to 60, from 25 to 60, from 20 to 80, from 1 to 7 Torr, or from 1 to 1 Torr of plasticizer. . Of course, as long as it is suitable for a particular application, other quantities can be used. In some embodiments, the plasticizer has a hydrocarbon segment of less than 2, less than 、, less than 12, or less than 10 carbon atoms. The amount of plasticizer can be adjusted to affect the glass transition temperature (Tg) of the poly(vinyl butyral) layer. In one case, a larger amount of plasticizer can be added to lower the Tg. To form a polymer layer, any suitable plasticizer may be added to the plasticizer used in the polymer layer of the polymer of the present invention, which may comprise a polybasic acid ester or polyol. Suitable plasticizers include, for example, diethylene glycol di-(2-ethylbutyrate), triethylene glycol dioxane 2_ethylhex IS day) ethyl acetate diheptanoate 'tetraethylene Alcohol hexanoic acid ester, hexamethylene hexyl sulphide, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of hexamethylene® thioheptyl® hydrazine and hydrazine, diisoindole adipic acid Base, heptyl adipate, dibutyl sebacate, agglomerates such as oil-modified sebacate S. a plasticizer, such as a mixture of succinic acid S and adipic acid disclosed in U.S. Patent No. 3,84,89, such as the adipate disclosed in U.S. Patent No. 4,144,217, And mixtures and compositions of the above. Other plasticizers which may be used are the mixed adipates of G to C9 alkanols and (4 to Cl Cycloalkanols (as disclosed in U.S. Patent No. 5,013,779), 147287.doc 201132498 and <: 6 to (8 hexyl acrylate) such as hexyl adipate. In various embodiments, the plasticizer used is dihexyl adipate and/or triethylene glycol di_2_ethyl The poly(vinyl butyric acid) polymer, the plasticizer, and any additives may be heat treated and disposed in the form of flakes according to methods known to those of ordinary skill in the art. Forming - poly(vinyl butyral) An exemplary method of flaking includes extruding molten poly(vinyl butyral) by forcing the melt through a mold (eg, a mold having a dimension that is substantially larger than the opening of the vertical dimension) (which includes Another exemplary method of forming a poly(vinyl butyral) sheet from a plasticizer, and a plurality of additives, comprises casting a melt from a mold into a roll, curing the resin, and substantially removing the cured resin in the form of a sheet. In various embodiments, the polymer layer can There are, for example, 〇1 to 25 mm, 0.2 to 2.0 mm, 〇·25 to 1_75 mm, and 〇.3 to 1.5 mm thickness. The poly(ethylene butyl butyrate) layer of the present invention may contain a ring of low molecular weight. Oxygen resin additives are known in the art (for example, see U.S. Patent Nos. 5,529,848 and 5,529,849), any suitable epoxy resin agent can be used with the present invention. Other additives can be incorporated into the polymer sheet. To improve its performance in the final product. Such additives include, but are not limited to, dyes, pigments, stabilizers (such as 'UV stabilizers), antioxidants, anti-blocking agents, and additional infrared absorption. Agents, flame retardants, combinations of the above additives, and the like. Typical UV stabilizers include substituted 2 Η-stupid triazoles, such as those by Ciba Specialty Company, 147287.doc 201132498
TinUVm之商標名販售，（舉例而言）Tinuvin328®，如式 所示.： ^ 11The brand name of TinUVm is sold, for example, Tinuvin328®, as shown in the figure.: ^ 11
基底基板 本發明之基底基板（其在圖丨中係以元件丨2展示）可為。 形成本發明之光伏打裝置於上之任何合適基板。實例包i (但不限於）玻璃，及硬質塑膠玻璃材料（其產生「硬質」薄 膜模組），及薄塑膠膜諸如聚對苯二曱酸乙二酯、聚醯= 胺、含氟聚合物，及類似物（其等產生「可撓性」薄犋模 組）。一般較佳係該基底基板允許大多數35〇至12〇〇奈米範 圍之入射輻射穿透，但熟習此項技術者應認知可有若干^ 化例，包含光經由保護基板進入光伏打裝置之變化例。— 薄膜光伏打裝置 本發明之薄膜光伏打裝置（其在圖丨中係以元件14展示） 係直接形成於基底基板上。典型的裝置製造包括沈積第一 導電層；蝕刻該第一導電層；沈積及蝕刻半導體層；沈積 第一導電層，蝕刻該第二導電層；及取決於應用而應用匯 流排導體及保護層。一電絕緣層可視情況地形成於第一導 電層與該基底基板之間基底基板上。此選用層可為（例如 I47287.doc 10 201132498 一石夕層。 儘管本發明之m-苯并三唾劑可添加至聚合物層以用於 無任何銀之光伏打裝置上，在較佳實施例中，ih_苯并三 唾係用於聚（乙烯縮丁酸）層中，該層係用於—具有包括銀 之光伏打裝置之光伏打模組t。銀組件之實例包含（但不 限於）導電層或元件（諸如線栅）或反射層（例如，參見美國 2006/0213548)。 、 本發明之1H-苯并三唑劑可添加至聚 在其他實施例中 合物層巾以用於包含經過降解之其他金属之力伏打裝置 上，其中該等金屬包含(例如)鉍、銅、鎘、鉛、錫、鋅、 金、銦、鈀、鉑、鋁、銻、鉻、鐵、鎳、鍺、钽、鈦，或 釩0 熟習此項技術者應認知上述裝置製造僅是一種已知方法 且僅是-本發明之實施例。許多其他類型的薄膜光伏打裝 置係在本發明之範疇内。形成方法及裝置之實例包含彼等 美國專利文獻 2003/(H80983、7,074,641、6,455,347、 6,500,690、2006/0005874、2007/0235073、7,271，333，及 2002/0034645中所描述之該等形成方法及裝置。 薄膜光伏打裝置之各種組件可經由任何合適的方法形 成。在各種實施例中，可使用化學氣相沈積（CVD)、物理 氣相沈積（PVD)及/或濺鍍。 上述兩個導電層係用作為電極以運送由居間半導體材料 所產生的電流。該等電極中之一者一般係透明的以允許太 陽輻射線到達半導體材料。當然，可兩導體皆係透明，或 147287.doc •11· 201132498 其中一導體可係反射性，使得已通過半導體材料之光反射 回至該半導體材料内。導電層可包括任何合適的導電氧化 物材料，諸如氧化錫或氧化鋅，或若透明度（諸如）對「背 面」電極而言不重要，則可使用金屬或金屬合金層，諸如 泫等包括鋁或銀者。在其他實施例中，可組合一金屬氧化 物層與金屬層以形成一電極，且該金屬氧化物層可摻雜有 硼或鋁並使用低壓化學氣相沈積進行沈積。該等導電層的 厚度可為（例如）〇. 1微米至i 0微米。 薄膜光伏打裝置之光伏打區可包括（例如）習知piN或pN 結構的氫化非晶矽。該矽的厚度通常可高達約5〇〇奈米， 其通常包括一具有3至25奈米之厚度之Ρ·層、一20至450奈 米之i-層，及一 20至40奈米之n-層。例如，如美國專利第 4,〇64,521號中所述’可藉於矽烷或矽烷與氫之混合物中輝 光放電的方式沈積。 或者，半導體材料可為微非晶矽、碲化鎘（CdTe或 CdS/CdTe)、二硒化銅銦（CuInSe2，或「CIS」，或 CdS/CuInSe2) ' 硒化銅銦鎵（CuInGaSe2或「CIGS」），或其 他光伏打活性材料。本發明之光伏打裝置可具有額外半導 體層’或上述半導體類型之組合且可為一串聯、三接點或 異質接面結構。 蝕刻該等層以形成該裝置之個別組件可使用任何習知半 導體製造技術進行，該等習知技術包含（但不限於）使用光 阻劑遮罩進行絲網印刷、使用正性或負性光阻蝕刻、機械 劃線、放電劃線、化學蝕刻，或雷射蝕刻。典型地，蝕刻 147287.doc 12 201132498 各種層將導致裝置内個別光電池的形成。該等裝置可使用 在製程之任何合適階段插入或形成的匯流條而電連接至其 他裝置。 在與聚（乙烯縮丁醛）層及保護基板裝配之前，一保護層 可視情況地形成於光電池上。該保護層可為（例如）經濺鍍 之鋁。 形成自選用絕緣層、該等導電層、該等半導體層，及選 用保護層之該等電互連光電池形成本發明之光伏打裝置。 保護基板 本發明之保護基板（其在圖〗中係以元件丨8展示）可為任 何月t夠用於結合聚合物層且充分保護該下伏裝置之合適基 板。實例包含（但不限於）玻璃、硬質塑膠，及薄塑膠膜^ 如聚（對苯二曱酸乙二酯）、聚醯亞胺、含氟聚合物，及類 似物。一般較佳地是該保護基板允許大多數35〇至12⑻奈 米範圍之入射輻射穿透，但熟習此項技術者應認知可能有 若干變化例，包含所有進入光伏打裝置之光係經由基底基 板進入之變化例。在此等實施例中，保護基板不必係透明 的，或大部分如此，且可為（例如）一阻止光經由該保護基 板離開光伏打模組之反射膜。 裝配 本發明之薄膜光伏打模組之最終裝配包括設置一聚（乙 浠縮丁酸·）層，其係使用已形成於一基底基板上之若干匯 流條（若可用）而與一薄膜光伏打裝置接觸；設置一與聚（乙 烯縮丁醛）層接觸之保護基板，及層壓該裝配以形成該模 147287.doc 201132498 組。 雖然本申請案之主體已使用所例示之該等較佳實施例設 計，但是本發明於其範疇内包含所有包括銀組件及聚（乙 烯縮丁醛）之光伏打裝置，包含標準（非薄膜）光伏打裝置， 以及此項技術中廣為人知的其他包括與一可降解金屬組件 (例如，太陽能玻璃，及鏡子）接觸之聚乙烯縮丁醛薄片之 多層層壓板。 本發明包含聚（乙烯縮丁醛）薄片，其具有併入1H_苯并 二。坐且視情況併入本文中描述之任何其他添加劑之本文中 所描述的任何組件。 本發明包含一種製造光伏打模組的方法，其包括以不步 驟.供一基底基板，於其上形成本發明之一光伏打裝 置；及使用一本發明之聚（乙烯縮丁醛）層層壓該光伏打裝 置至一保護基板上。 本發明包含若干包括本發明之聚合物層的光伏打模組。 實例 實例1 使用一小型實驗室規模的擠壓機；將750克具有約187 wt·%之乙烯醇含量及0·5 wt %至4 wt.%之乙酸乙烯酯殘餘 量之聚（乙烯縮丁搭）樹脂與285克作為增塑劑之三乙二醇 二-(2-乙基己酸酯）、2 63克紫外線吸收劑Tinuvin328⑧、 0· 1 9克作為黏著控制鹽之（2_乙基丁酸）鎂，及如表1中所展 示各種添加劑混合；及擠壓成〇76毫米厚度的薄片。 該等薄片係用於層壓一薄膜太陽能電池（15xl5釐米）。 147287.doc 14 201132498 該等層壓板係在1，〇〇〇伏特偏壓下曝露於85°c及85%相對濕 度中1，000小時。層壓板之黃色指數係在1，000小時曝露後 量得。層壓板之典型黃色指數在曝露之前係約12(11與13 之間）。 表1 樣本 編號 添加劑 添加劑 重量 1，000小時後的 黃色指數 控制#1 無 無 122.2 1 1H-苯并三唑 1.875 克 27.1 2 Anox 70®(2,2'-硫二伸乙基雙[3-(3,5-二-第三 丁基-4-羥基苯基）丙酸酯]) 1.875 克 93.4 3 NaugardXL-l®(CAS 70331-94-1)苯丙酸、 3,5-雙(1,1-二甲基乙基)斗羥基-,1,Γ-[(1，2-二 側氧基-1，2-亞乙基)雙(亞胺基-2,1-亞乙基)] 酯 1.875 克 118.4 控制#2 無 無 110.8 4 IrganoxMD1024®苯丙酸、3,5-雙(1，1-二曱 基乙基)斗羥基-，2-[3-[3,5-雙(1,1 -二曱基乙 基)-4-羥基苯基]-1-側氧基丙基]醯肼(CAS 32687-78-8)Tinuvin 123® 癸二酸、1，10-雙 [2,2,6,6-四甲基-1-(辛氧基)-4-哌啶基]酯 (CAS 122586-52-1) 0.75 免 61.6 實例2 在一試量產規模之擠壓機中如下製備該等薄片（1.14毫米 厚）：對於每100克之聚（乙烯縮丁醛）樹脂，添加3 8克作為 增塑劑之三乙二醇二-(2-乙基己酸酯）、0.35克Tinuvin328®、 0.025克（2-乙基丁酸）鎂，以及表2中所展示的各種添加 劑。塗佈有銀及其他層之玻璃係用於製備聚（乙烯縮丁醛） 層壓板。經塗佈之玻璃的尺寸為7 X 9厘米。該等層壓板在 85°C、85%相對濕度（RH)以及1，000伏特之偏壓下進行測試 147287.doc -15- 201132498 670小時。 表2 樣本編號 聚（乙烯縮丁醛)調配物 (每100克聚(乙烯縮丁醛)樹脂） 黃色指數 t=0 t=670 小時 控制3 控制(無額外添加劑） 12.8 95.6 5 0.125克1H-苯并三唑 12.5 38.6 6 0.35克1H-苯并三唑 12.6 36.8 7 0.35克1H-苯并三唑與0.15克Anox 70® 12.6 35.7 8 0·35克IΓganoxMD1024®與0.15克Tinuvinl23® 11.2 79.1 實例3 實例1之控制#2及樣本4中銀的濃度係在1 000小時曝露之 後測得。使該等樣本層離。藉於75 : 25己烷/乙酸乙酯之 混合物中浸泡及攪拌而自該等層中提取出增塑劑。所回收 的聚（乙烯縮丁醛）樹脂保留顏色，接著溶於酸中並使用一 Perkin Elmer Optima 3300DV儀器分析銀含量。亦分析一 聚（乙烯縮丁醛）之標準薄片的銀含量。 表3 控制2 樣本4 標準聚 (乙烯縮丁醛） 銀 (ppm) 316 150 <5 「黃色指數」係在完整玻璃層壓板上量得。樣本係藉由 根據ASTM測試方法E 133 1排除鏡面組件之半球反射率（且 其中透明玻璃表面係面向光源）量得。使用整個可見光譜 的反射率值，黃色指數值係使用呈現於ASTM E3 1 3「塑膠 之黃色指數的標準測試方法」方法之表1中「黃色指數方 I47287.doc •16- 201132498 程式之係數」之「C，193 1」攔算得。 偏壓下的測試係藉由先形成以下構造而完成：電極/玻 璃層/光伏打膜/電極/聚（乙烯縮丁醛）/玻璃層。接著施加 1，0 0 0伏特直流之電壓，其導致約〇 1毫安培的電流。 如該等實例中所示般，式Π中所展示之Tinuvin328®、 經取代之2H-苯并三唾衍生物的添加無法阻止黃化，其突 顯1H-苯并三唑的顯著成功。 憑藉本發明’當利用含有銀之光伏打裝置時，現可能提 供具有極佳聚（乙烯縮丁醛）穩定性及黃化抗性的薄膜光伏 打模組。 雖然本發明已參考例示性實施例進行描述，但熟習此項 技術者應瞭解在不偏離本發明範疇的情況下，可進行各種 變化且等效物可取代其元件。此外，在不偏離本發明之基 本範4的情況下，可進行許多改良以使—特定狀況或材料 適合本發明之教示H不希望本發明受限於揭示為經 設計用於執行本發明之最佳模式的該等特定實施例，但本 發明將包含隨附中請專利範圍内的所有實施例。 應進-步瞭解’任何本發明之任何單一組件既定之範 圍、值，或特徵可於相容處與任何本發明之任何其他組件 既定之範圍1，或特徵互換使用以形成一具有各諸組件 定義值之實施例，如全文中所列般。例如，薄膜模组可包 括聚(乙烯縮丁酸)與若干光伏打元件之組合物以形成許多 本發明之範彆内的排列，但列表將極其繁瑣。 任何摘要或任何以專利範圍⑽提供的圖式參考數字 147287.doc 201132498 僅係用於說明目的且不應理解為將本發a 中所展示的任一特定實施例。 月限制於任何圖式 諸圖式未按比例繪製，除非另有指示。 將本文中所指之每一參考文獻，包含期刊文章 書、申請案，及書籍之全文以引用的方式併入本文中。1 【圖式簡單說明】 岡 1 表 , * 衣不—本發明之薄膜光伏打裝置之示意性戴面圖 【主要元件符號說明】 10 ^ 薄膜光伏打模組 12 ^ 基底基板 14 光伏打裝置 16 聚（乙烯縮丁醛）層 18 保護基板 147287.docBase substrate The base substrate of the present invention, which is shown in Figure 丨2, can be. Any suitable substrate on which the photovoltaic device of the present invention is formed. Examples include i (but not limited to) glass, and rigid plastic glass materials (which produce "hard" film modules), and thin plastic films such as polyethylene terephthalate, polyfluorene = amines, fluoropolymers , and the like (which produce a "flexible" thin tantalum module). It is generally preferred that the base substrate allows most of the incident radiation penetration in the range of 35 〇 to 12 〇〇 nanometers, but those skilled in the art will recognize that there are several examples of including light entering the photovoltaic device via the protective substrate. Change example. - Thin film photovoltaic device The thin film photovoltaic device of the present invention (which is shown in Figure 14 as component 14) is formed directly on the base substrate. A typical device fabrication includes depositing a first conductive layer; etching the first conductive layer; depositing and etching a semiconductor layer; depositing a first conductive layer, etching the second conductive layer; and applying a busbar conductor and a protective layer depending on the application. An electrically insulating layer is optionally formed on the base substrate between the first conductive layer and the base substrate. The optional layer can be (e.g., I47287.doc 10 201132498, a layer of stone. Although the m-benzotrisin of the present invention can be added to a polymer layer for use in a photovoltaic device without any silver, in a preferred embodiment Wherein ih_benzotrisole is used in a poly(ethylene butyric acid) layer for use in a photovoltaic module having a photovoltaic device comprising silver. Examples of silver components include (but are not limited to) a conductive layer or element (such as a wire grid) or a reflective layer (see, for example, US 2006/0213548). The 1H-benzotriazole agent of the present invention may be added to other embodiments to be used in a layered towel for use in a force voltaic device comprising degraded other metals, such as cerium, copper, cadmium, lead, tin, zinc, gold, indium, palladium, platinum, aluminum, lanthanum, chromium, iron, nickel , 锗, 钽, Titanium, or vanadium 0. Those skilled in the art will recognize that the above-described device fabrication is only one known method and is merely an embodiment of the invention. Many other types of thin film photovoltaic devices are within the scope of the present invention. Examples of forming methods and devices include their US patents The forming methods and apparatus described in 2003/(H80983, 7,074,641, 6,455,347, 6,500,690, 2006/0005874, 2007/0235073, 7,271,333, and 2002/0034645. The various components of the thin film photovoltaic device can be adapted via any suitable The method is formed. In various embodiments, chemical vapor deposition (CVD), physical vapor deposition (PVD), and/or sputtering can be used. The two conductive layers are used as electrodes to transport the intermediate semiconductor material. One of the electrodes is generally transparent to allow solar radiation to reach the semiconductor material. Of course, both conductors are transparent, or 147287.doc •11·201132498 One of the conductors can be reflective, such that Light is reflected back into the semiconductor material by the semiconductor material. The conductive layer can comprise any suitable conductive oxide material, such as tin oxide or zinc oxide, or if transparency, such as is not critical to the "back" electrode, A metal or metal alloy layer is used, such as tantalum or the like including aluminum or silver. In other embodiments, a metal oxide layer and a metal layer may be combined. An electrode is formed, and the metal oxide layer may be doped with boron or aluminum and deposited using low pressure chemical vapor deposition. The thickness of the conductive layers may be, for example, 〇. 1 μm to i 0 μm. The photovoltaic cell of the device may comprise, for example, a hydrogenated amorphous germanium of the conventional piN or pN structure. The germanium may typically have a thickness of up to about 5 nanometers, which typically comprises a thickness of from 3 to 25 nanometers. a layer, an i-layer of from 20 to 450 nm, and an n-layer of from 20 to 40 nm. For example, as described in U.S. Patent No. 4, No. 64,521, which may be derived from decane or decane and hydrogen. The glow discharge is deposited in the mixture. Alternatively, the semiconductor material may be micro-amorphous germanium, cadmium telluride (CdTe or CdS/CdTe), copper indium diselenide (CuInSe2, or "CIS", or CdS/CuInSe2) 'copper indium gallium selenide (CuInGaSe2 or " CIGS"), or other photovoltaic active materials. The photovoltaic device of the present invention may have an additional semiconductor layer' or a combination of the above semiconductor types and may be a series, triple junction or heterojunction structure. Etching the layers to form individual components of the device can be performed using any conventional semiconductor fabrication technique including, but not limited to, screen printing using a photoresist mask, using positive or negative light. Etch etching, mechanical scribing, discharge scribing, chemical etching, or laser etching. Typically, etching 147287.doc 12 201132498 various layers will result in the formation of individual photovoltaic cells within the device. The devices can be electrically connected to other devices using bus bars that are inserted or formed at any suitable stage of the process. A protective layer may optionally be formed on the photovoltaic cell prior to assembly with the poly(vinyl butyral) layer and the protective substrate. The protective layer can be, for example, sputtered aluminum. The electrically interconnected photovoltaic cells formed from the optional insulating layer, the conductive layers, the semiconductor layers, and the optional protective layer form the photovoltaic device of the present invention. Protecting the Substrate The protective substrate of the present invention, which is shown in Figure VIII, can be any suitable substrate for any month to bond the polymer layer and adequately protect the underlying device. Examples include, but are not limited to, glass, rigid plastic, and thin plastic films such as poly(ethylene terephthalate), polyimine, fluoropolymers, and the like. It is generally preferred that the protective substrate allows for most of the incident radiation penetration in the range of 35 〇 to 12 (8) nm, but those skilled in the art will recognize that there may be several variations, including all of the light entering the photovoltaic device via the base substrate. Enter the change example. In such embodiments, the protective substrate need not be transparent, or mostly such, and may be, for example, a reflective film that blocks light from exiting the photovoltaic module via the protective substrate. The final assembly of the assembled thin film photovoltaic module of the present invention comprises the provision of a poly(ethylformal butyrate) layer which is bonded to a thin film photovoltaic using a plurality of bus bars (if available) formed on a base substrate. The device is in contact; a protective substrate in contact with the poly(vinyl butyral) layer is disposed, and the assembly is laminated to form the mold 147287.doc 201132498. Although the subject matter of the present application has been designed using the preferred embodiments illustrated, the invention includes within its scope all photovoltaic devices including silver components and poly(vinyl butyral), including standard (non-film) Photovoltaic devices, and other multilayer laminates of polyvinyl butyral sheets that are well known in the art and that are in contact with a degradable metal component (e.g., solar glass, and mirrors). The present invention comprises a poly(vinyl butyral) sheet having incorporated 1H_benzo. Any of the components described herein that sit and optionally incorporate any of the other additives described herein. The present invention comprises a method of manufacturing a photovoltaic module comprising: providing a substrate substrate on which a photovoltaic device of the present invention is formed; and using a poly(vinyl butyral) layer of the present invention Pressing the photovoltaic device onto a protective substrate. The invention comprises a plurality of photovoltaic modules comprising the polymer layer of the invention. EXAMPLES Example 1 A small laboratory scale extruder was used; 750 grams of polyvinyl acetate having a vinyl alcohol content of about 187 wt.% and a residual amount of vinyl acetate of from 0.5 to 4 wt.%. Resin with 285 g of triethylene glycol di-(2-ethylhexanoate) as a plasticizer, 2 63 g of UV absorber Tinuvin 3288, 0.19 g as adhesion control salt (2-ethyl) Magnesium butyrate, and various additives as shown in Table 1 were mixed; and extruded into a sheet having a thickness of 76 mm. The sheets were used to laminate a thin film solar cell (15 x 15 cm). 147287.doc 14 201132498 The laminates were exposed to 85 ° C and 85% relative humidity for 1,000 hours at a 〇〇〇 volt bias. The yellow index of the laminate was measured after 1,000 hours of exposure. The typical yellowness index of the laminate is about 12 (between 11 and 13) prior to exposure. Table 1 Sample No. Additives Weight Yellow Index Control after 1,000 hours Weight #1 None No 122.2 1 1H-Benzotriazole 1.875 g 27.1 2 Anox 70® (2,2'-thiodiethylidene double [3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate]) 1.875 g 93.4 3 Naugard XL-l® (CAS 70331-94-1) phenylpropionic acid, 3,5-double (1 , 1-dimethylethyl) hydroxy-, 1, fluorene-[(1,2-di-oxy-1,2-ethylene) bis(imino-2,1-ethylene) ] ester 1.875 g 118.4 control #2 no 110.8 4 IrganoxMD1024® phenylpropionic acid, 3,5-bis(1,1-didecylethyl) hydroxy-, 2-[3-[3,5-double ( 1,1 -didecylethyl)-4-hydroxyphenyl]-1-oxopropyl]oxime (CAS 32687-78-8) Tinuvin 123® azelaic acid, 1,10-double [2 , 2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl]ester (CAS 122586-52-1) 0.75 exempt 61.6 Example 2 In a trial production scale extruder The sheets (1.14 mm thick) were prepared as follows: For every 100 grams of poly(vinyl butyral) resin, 38 grams of triethylene glycol di-(2-ethylhexanoate), 0.35 was added as a plasticizer.克 Tinuvin328®, 0.025 g (magnesium 2-ethylbutyrate), And various additives shown in Table 2. Glass coated with silver and other layers is used to prepare poly(vinyl butyral) laminates. The coated glass has a size of 7 x 9 cm. The laminates were tested at 85 ° C, 85% relative humidity (RH) and a bias of 1,000 volts 147287.doc -15- 201132498 670 hours. Table 2 Sample No. Poly(vinyl butyral) formulation (per 100 g of poly(vinyl butyral) resin) Yellow index t=0 t=670 hours Control 3 Control (no additional additives) 12.8 95.6 5 0.125 g 1H- Benzotriazole 12.5 38.6 6 0.35 g 1H-benzotriazole 12.6 36.8 7 0.35 g 1H-benzotriazole and 0.15 g Anox 70® 12.6 35.7 8 0·35 g IΓganox MD1024® and 0.15 g Tinuvinl23® 11.2 79.1 Example 3 The concentrations of silver in Control #2 and Sample 4 of Example 1 were measured after 1000 hours of exposure. The samples are delaminated. The plasticizer was extracted from the layers by soaking and stirring in a 75:25 hexane/ethyl acetate mixture. The recovered poly(vinyl butyral) resin retained color, then was dissolved in acid and analyzed for silver content using a Perkin Elmer Optima 3300 DV instrument. The silver content of a standard sheet of poly(vinyl butyral) was also analyzed. Table 3 Control 2 Sample 4 Standard Poly(vinyl butyral) Silver (ppm) 316 150 < 5 "Yellow Index" was measured on a complete glass laminate. The sample was measured by excluding the hemispherical reflectance of the mirror assembly (and wherein the transparent glass surface was facing the light source) according to ASTM Test Method E 133 1. Using the reflectance values of the entire visible spectrum, the yellow index values are shown in Table 1 of the ASTM E3 13 "Standard Test Method for Plastic Yellow Index" method. "Yellow Index Side I47287.doc •16-201132498 Coefficient of Program" "C, 193 1" is calculated. The test under bias is accomplished by first forming the following structure: electrode/glass layer/photovoltaic film/electrode/poly(vinyl butyral)/glass layer. A voltage of 1,0 volts volts is then applied, which results in a current of about 1 milliamperes. As shown in these examples, the addition of Tinuvin 328®, a substituted 2H-benzotrisin derivative, as shown in the formula, did not prevent yellowing, which highlighted the significant success of 1H-benzotriazole. By virtue of the present invention, when a photovoltaic device containing silver is utilized, it is now possible to provide a thin film photovoltaic module having excellent poly(vinyl butyral) stability and yellowing resistance. While the invention has been described with respect to the embodiments of the invention, it is understood that those skilled in the In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the basic scope of the invention. These particular embodiments of the preferred mode, but the invention will include all embodiments within the scope of the appended claims. It should be further understood that the scope, value, or characteristics of any single component of any of the present invention can be used interchangeably with any of the other components of the present invention within the scope of the scope, or the features are used interchangeably to form a component. Examples of defined values, as listed throughout. For example, a film module can include a combination of poly(vinyl butyric acid) and a plurality of photovoltaic elements to form a plurality of arrangements within the scope of the invention, but the listing will be extremely cumbersome. Any abstract or any reference number 147287.doc 201132498, which is provided by the scope of the patent (10), is for illustrative purposes only and should not be construed as any particular embodiment shown in the present invention. Months are limited to any drawing. Figures are not drawn to scale unless otherwise indicated. Each of the references referred to herein, including journal articles, applications, and books is hereby incorporated by reference in its entirety. 1 [Simple description of the diagram] 冈1表, *衣不不—Summary surface diagram of the thin film photovoltaic device of the present invention [Major component symbol description] 10 ^ Thin film photovoltaic module 12 ^ Base substrate 14 Photovoltaic device 16 Poly(vinyl butyral) layer 18 protective substrate 147287.doc