201123314 六、發明說明： 【發明所屬之技術領域】 本發明總體上涉及光伏技術。更具體地，本發明提供了—種 用於使用銅銦二硒化物物質（或硒化銦銅，CIS)、銅麵嫁二石西化 物物質（或銅銦鎵硒’ CIGS)和/或其他物質的薄膜光伏裝置的方 法和結構。本發明可應用於光伏模組、柔性片、建築物或窗戶的 玻璃、汽車等。 【先前技術】 在製造CIS和/或CIGS類型的薄膜的過程中，存在各種製造 上的難題’例如，保持基板材料的結構完整性，確保薄膜材料的 均勻性和細微性等。雖然過去的傳統技術已經解決了這些問題中 的一些，但是其在許多情況下經常是不夠的。其中，用來製造as 和/或CIGS薄膜的系統（例如，處理室）通常難於清洗。因此， 期望改進的用於製造薄膜光伏裝置的系統和方法。 【發明内容】 本發明總體上涉及光伏技術。更具體地，本發明提供了一種 用於使用銅銦二硒化物物質（CIS)、銅銦鎵二硒化物物質（CIGS) 和/或其他物質的薄膜光伏裝置的方法和結構。本發明可應用於光 伏模組、柔性片、建築物或窗戶的玻璃、汽車等。 根據一種實施方式，本發明提供了一種利用自清潔熔爐製造 銅銦二硒半導體膜的方法。該方法包括將多個基板轉移至熔爐 中，熔爐包括處理區域和至少一個與處理區域可拆卸接合的端帽 區域，將多個基板中的每一個相對於重力方向垂直定向而設置， 用數字N限定多個基板，其中N大於5，每個基板具有銅和銦複 合結構。該方法還包括將包括氫物質和硒化物物質以及載氣的氣 態物質引入熔爐中，並將熱能轉移入熔爐中以使溫度從第一溫度 201123314 升南，第二溫度’第二溫度的範圍是從約Μ。。。到約·。。，從 而在每個基板上至少開始她和銦複合結構形細銦二砸膜。該 方法進-步包括使_的處龍域的内部區域的殘獅化物物質 2。該方法進—步包括在可在第三溫度下操作的端帽區域的附 ^儿積元素则匕物物質（elemental selenide species)。而且，該方 ί包括’通過至少從處觀域的㈣區域分解殘餘的砸化物物 質’將内部區域保持為基本上沒有元素石西化物物質。 在-種具體實施方式中，在_中㈣靴氫氣體作為工作 =度為4GG°C左右或更高時，熱啟動砸化氫氣體以使其 :、解，形成讀砸（Se)或碼簇（Se2或Se3)。端帽區域包括蓋子， 動:水進行冷卻並用燈進行加熱來控制蓋子的溫度。監測 =的=度保持冷卻以用作‘‘低溫果”，使得可在蓋子上沉積砸物 f (7C素砸和補）’並抑制砸和其他膜材料（例如鋼）之間的反 應。在完成-個或多個處理迴圈之後，可用布（例如 材料）進一步清潔端帽區域的蓋子以去除沉積_殘餘物 1該理解，本發明提供了許多優於常規技術的益處。盆中， 本毛明的錢和方法鋪齡統相容， _ 各種實施方式中，將殘餘氣體合併入處 ^ =本。在 能夠容易地進行清洗。此外還具有其他的^特仏域中’從而 【實施方式】 本發明總體上涉及光伏技術。更具體地， 用於使用銅銦二雜物物質（CIS )、銅銦鎵二靴㈣^ /'種 和/或其他的薄膜光伏裝置的方法和結構。 4、( ^) 組、柔性片、建築或窗戶的玻璃、汽車等。了應用於光伏模 圖^是根據本發明的-種實施方式的具有重疊電極層的透明 201123314 基板的簡圖。此圖僅是一個實施例，在本文中其不應限制權利要 求的範圍。如所示出的，結構100包括透明基板1〇4。在一種實施 方式中，基板104可以是玻璃基板，例如鈉舞玻璃。然而，也可 使用其他類型的基板。基板的實例包括硼矽玻璃、丙烯酸玻璃、 糖玻璃、特製Coming™玻璃等《如所示出的，在基板1〇4上沉積 包含金屬電極層102的接觸層。根據一種實施方式，金屬電極層 102包含特徵在於具有基於太陽能電池應用的薄膜是最佳的預定 導電率的金屬材料。根據應㈣況’可4種方式沉積金屬電極 層102。例如，金屬電極層102主要包括通過濺射來沉積的鉬膜。 例如，厚度的範圍可以是200至700 nm。可以使用濺射裝置（例 如，直流磁控管濺射裝置）在基板上沉積材料的薄膜。這種裝置 是公知的，並且可商購獲得。但是，應該理解，也可以使用其他 類型的設備和/或方法，例如，在基於真空的環境中蒸發。作為一 個實施例，下面描述濺射沉積方法。 ‘ 濺射沉積是通過從“靶（目標），，或源濺射或噴射材料，然後 將其沉積在基板（例如，矽晶片或玻璃）上來沉積薄膜的物理氣 相沉積（PVD)方法。從靶噴射的所濺射的原子具有較寬的能量 分佈，典型地高達數10 eV ( 100000 κ)。通過改變背景氣壓，可 獲得從高能量彈道衝擊到低能量熱運動的整個範圍。濺射氣體通 常是惰性氣體，例如氬。為了有效地實施動量轉移，濺射氣體的 原子量應接近靶的原子量，因此，對於濺射輕元素來說，優選氖， 而對於重元素來說則使用氪或氣。也可以使用反應性氣體來賤射 化合物。根據i藝參數，可在絲面上、在飛行巾或在基板上形 成化合物。控制濺射沉積的許多參數的可用性使得其是一個複^ 過程，但也使得熟練的技術人員能夠在很大程度上控制臈的生長 和微結構。 6 201123314 圖2是根據本發明的—種實施方式的包括銅和銦材料的複合 ，構的簡圖。此圖僅是—個實例，在本文中不應限制權利要求的 範圍。在此實施方式中’結構2〇〇包括玻璃基板2〇8，優選納辦玻 璃’其厚度約為1至3 mm。例如，玻璃基板2〇8用作支撐層。在 基板挪上沉積金屬層施。例如，金屬層施用作金屬電^層以 ，供電接觸。例如，層206主要包括已經通過絲而沉積的賴， j度為200至700 nm。在一種具體實施方式中，在玻璃挪上 冗積初始鉻膜。例如’提供鉻層以確保整個結構與基板208 的良好枯接。_層中也可使用其他類型的材料，例如二氧化石夕、 亂化石夕等。層204和202主要包括通過濺射處理而沉積在 =上的銅層和銦層。如圖2所示，銦層覆蓋銅層。但是應該理解曰， ^可^採用其他佈置。在另—實施方式中，銅層覆蓋銦層。作為 一個實例’職雜置（例如，直流磁控管濺射裝置）在 ^積材料的薄膜（例如層2〇2、綱和/或施）。應該理解，可以 型的濺射裝置。這種裝置是公知的並且是可商購的。 他材料。應該理解，在本申請的全文中贿的技術是 二 > 運_ ’並且也可以使用其他類型的設備和/或方法，例如， ，基於真空的環境中蒸發來沉積銅和銦材料。在某些實施 :除了銅和鋼材料以外，可以形成沉積的錄材料 ^ 〇9=據_種實施方式，銅和銦材料之比小於κ = 〇·96) ’即’每一份銦材料中少於一份的銅。 為-個實施例，通過處理結構100來形成結構綱。例如， 沉積Cu和Ιη以形成結構20G。如上所述， :為在施方式中，Cu膜和In膜 處理的過程中形成㈤n複合物或Cu/In合:圖: 201123314 ^全文中描述的技術是可訪獅的，並 ㈣。u此真空的環境中蒸發來沉積銅和銦 ’ S二實也方式中，除了銅和銦材料外 的鎵材料（圖2中未示出）。 乂心成，儿積 疋根據本發日㈣另—實施方式的包括銅和銦複合薄膜 的複合結構训的簡圖。此圖僅是-個實例，其在本文中不2 ==Γ其Γ斤示出的，結構210包括透明基板216:在 ，back contact) 極層214。例如’層214主要包括通過濺射而沉積的崎料的膜。 在-種具體實施方式中，在沉目材料之前在玻璃216上沉積初 始的鉻膜，以提供整個結構與基板21〇的良好的祕。層M2主 要包括銅銦合金或細複合㈣。例如，細的混合或合金化導 致複合銅銦膜的均勻性或有利的形態得到改進。在魏步驟之 後，將此改進的結構載入到期望的CIS膜中。根據一種實施方式， 由擴散到彼此之中的銅和銦材料的單獨的層形成銅銦合金材料。 例如’能夠通過使該結構經受高溫來促進形成細合金材料的處 理。 圖3是根據本發明的一種實施方式的熔爐的簡圖。此圖僅是 -個實施例，其在本文中不應限制申請專利範圍。如所示出的， 熔爐300包括處理室302和室的端帽3〇4。根據一種實施方式，反 應室302的特徵在於大於2〇❶升的容積。將處理室3〇2的内表面 和空間區域描述為内部處理區域32〇。在一種實施方式中，處理室 302可包括石英管。端帽區域322代表端帽3〇4的内表面和部分地 暴露於内部處理區域320的管子附近的表面。在一種實施方式中， 端帽304可由金屬材料製成。在某些實施方式中，端帽3〇4和處 8 201123314 ”不同的表面反應性、導熱率、祕、和/或 L 各種類型的材料都可以沉積在端帽304 腔室撕露於樣品或將要裝載於腔室#的基板的 送機.，料空泵频包㈣齡子泵⑽和ί轉泵 的方式來Α线送機可财顧增㈣和幹泵的組合 、、主氣;如，如果特糾應用和/或處理需要，則可經由 氣Ϊ二I f料氣體和域稀釋氣體(例如，氦氣、氮氣、氬 =或，乳）引入處理室3〇2。用渦輪分子泵31()經由旋轉栗312 =至302抽真空，旋轉泵312經由閘閥和傳導間318與歧管训 室30^^’ ^歧管中或在反應炼爐中沒有專用的隔板。在反應 至02的外部安裝加熱元件3❶6。 可用於許多應用。根據一種實施方式，用雜300 _ ^麵型的基板施加熱能，並且用於51入各種類型的氣態 質。在-種實施方式中’在腔室搬的中心附近垂直地定位一 個或多個玻璃板或基板。作為一個實例，基板3()8可與圖2和圖 2A中描述_餘似（例如，在基板上覆蓋金屬接_的 曰或複=Cu/In層）。在包含砸的氣體（例如，存在的情況 下將這些層放在處理室中。在對材料進行給定時間段的退火之 後’銅、銦和雖此擴散並發生反應，以形成高品質的銅銦二砸 化物（CIS)膜。 圖4是根據本發明的一種實施方式的用於形成銅銦二硒化物 層的過私的簡圖。此圖僅是—個實例，其在本文中不應限制權利 要求的範圍。本領域普通技術人員將認識到許多其他變型、修改 矛暑代方式。還應5玄理解，本文中描述的實施例和實施方式僅用 201123314 於示意性目的，而且對於本領域的技術人員來說，暗示了能 此進行各種修改或變化，這些修改和變化均包括在本方法的 和範圍以及所附申請專利範圍内。 月 如圖4所示，可簡要地概括本方法以下。 1. 開始； 2. 提供多個具有銅和銦複合結構的基板； 3. 將包括氫物質和硒物質以及載氣的氣態物質引入熔爐中； 4. 將熱能轉移入熔爐中，以使溫度從第一溫度升高至第二溫度. 5. 使溫度保持在約第二溫度一段時間； 6. 使熔爐的處理區域的内部區域的任何殘餘的硒化物物質分解； 7. 將溫度降至第三溫度； 8. 使溫度保持在約第三溫度一段時間； 9. 在可在第二溫度下操作的端帽區域的附近内沉積元素碼物質； 10. 將溫度從第三溫度坡度降低至大約第一溫度； 11. 去除氣體；以及 12. 停止。 這些步驟僅是實施例，而不應限制本發明申請專利範圍。本 領域普通技術人員將認識到許多其他變型、修改和替代方式。例 如，當在本發明的範圍内考慮時，可以增加、去除、修改、重新 安排、重複和/或重疊以上略述的各種步驟。如所示出的，方法4〇〇 從開始步驟402開始。在此，該方法的使用者以處理室例如上文 中提到的、以及其他的步驟開始。在實施本方法之前，可將處理 201123314 室保持在大約室溫。 —步驟402是將多個基板轉移入處理室中。可將多個基板中的 母個相對於重力垂直定向而設置。可用數字N限定多個基板， 其中N大於5。此多個基板可以包括5個或更多個單獨的基板。 在另一實施方式中’此多個基板可包括40個或更多個單獨的基 板。例如’每個基板的尺寸可以是約65 _65咖。將每個基板 保持為基本平_結構，沒有翹曲賴壞。例如，如果將基板設 置在除了姉於重力垂直的方向以外的方向上，那麼重力就會導 致基板下錄翹曲。當基板㈣達職化溫度時會出現這種情 況’危及基板的結構完整性。典型地，玻璃基板，尤其是納舰 璃基板’在彻。(：（通常稱為應變點）時開始變軟。在—種實施方 式中’基板也根據預定間隔而彼此隔離，以確保均勻加歸與將 要引入熔爐的氣態物質的反應。 在縣板定位在處理室中之後，在步驟彻+，將氣態物質 (包括氫物質、碼物質、和/或載氣）引入處理室中。在一種實施 方式中氣Μ勿貝至少包括碼化物物質（例如，H2Se)和減。 在另:實f方式中，氣態物質包括其他類型的化學惰性氣體，例 如，虱、乳等。例如，將基板放在含砸的氣體（例如，H2Se)中。 然後在步驟4〇8，，將溶爐加熱至溫度範圍為約现乂到 450〇C的第二溫度。為了加熱處理室，可通過加減件、加熱線圈 等來實現熱能的轉移。例如，在步驟綱中，至少開始通過氣態 物質與每個基板上的銅和銦複合（或分層）結構之_反應來形 201123314 成銅銦二靴物膜。在-種具體實施方式中，銅和銦材料的分開 的層擴散至彼此之中，以形成單層銅銦合金材料。在步驟训中二 在熱處理間隔中，將第二溫度保持在3賞和4挪之間持續約 H)至60分鐘（時間段）。在另—實施方式中，第二溫度的範圍可 以為390〇C到410〇C。例如，步驟41〇提供的用於保持溫度的時 間段使得能夠形成as赌料。隨著溫度的升高，_内部的壓 力也會增加。在-種具體實施方式中，用壓力釋放_雜内部 的壓力保持在約650托。 在-種實施方式中，在溫度從第一溫度崎（ramping)至第 二溫度並在第二溫度達到穩定的過程中，晒化氫购會被部分地 熱裂解為Η原子和Se蒸氣。可以在—個或多個處財部分地去除 Se条耽。例如，可安裝低溫|，以從腔室卡直接抽出&蒸氣。在 另-實施财’冷卻_面帽可以_低棘的伽，以吸收或 冷凝由從熱的室内處職域至冷卻_帽區域的對流所攜帶的^ 蒸氣或Se簇，有效地抽出硒物質。 在溫度保持的過程中（步驟41〇)，在步驟412中，開始附加 地去除殘餘的魏物物質。在步驟414中，通過真空踩處理室 中形成真空。在-種具體實施方式巾，可_進行殘餘德物去 除處理’㈣如在以上段落中建議的處理室處於真空構造中為 止。在步驟416巾’-旦在處理室中產生真空（步驟414)，就引 入硫化氫（H2S)物質。處於第二溫度穩定水準的所引人的秘會 導致與包含摘銦複合财的崎質較換反應。例如，會發生 201123314 以下反應，CUInSe2 + H2S — CuInSexS| x+物，從基板上的膜部 分地去除Se ’並在腔室内的環境中重新產生聯。同時，可由從 熱反應室到包括端域蚊冷的區域的雌連續地運輸&顆粒 或、”田私’使付其可％積在端帽表面上，保持反應室基本沒有元素 砸在已經改I炼爐中的氣體環境以使得砸化物物質被去除並引 入硫化氫物質之後’開始第二溫餘升處理，步驟418。在一種具 體實施方式中，起到載氣作用的氮氣與靴物物質-起引入。將 炫爐的溫度升高至約5〇〇QC到525χ範圍的第三溫度。例如，為 了使溶爐中的疏化氫物質和基板之間發生反應而校準第三溫度。 在一種優選實施方式中，由於金屬端帽綱具有更高的熱導率， 金屬端帽304比石英處理室繼冷卻地快得多。甚至當腔室管加2 是熱的時，金屬端帽3〇4也能夠保持“冷卻,，（基本上在2〇〇〇c之 下）。產生溫度梯度’這在内部處理區域32()内產生對流。結果， 碼和/或其他殘餘物料並沉積在端紅。在—種频實施方式 中，如上所述的溶爐3⑽具有可單獨控制的加熱單元，其用來保 持炫爐内的溫度均勻度。例如，這些加熱器也可絲產生溫差， 該溫差導致參/或其他殘餘物機至端帽區域。 在步驟420 ’將溫度保持在第三溫度一定時間段，直到完成 CIS層的形成為止。根據從銅銦二砸化物膜提取出—種或多種石西物 質的目的’③置在包括硫物質的賴的環境巾在關隔時的保持 時間。去除預定量的雜質是有益的。在—種具體實施方式中， 從膜去除大約5%_，並用大約5%的硫代替。根據一種實施方 201123314 式，希望在砸材料和CIS膜之間進行完全的反應 。在步驟422中， 在去除蝴質錢，開始進行可控的溫度坡度下降處理。在步驟 」中將炼爐冷部至大約室溫的第一溫度，並從溶爐去除剩餘的 乱態物質。例如’用真空栗送機去除氣態物質。可在圖$㈤ 度分佈中示出上述溫度序列。 恤 在v驟420 + ’在分解殘餘的石西化物物質之後，開始進行浪 度坡度下降處理。㈣爐冷卻至大約室溫的第—溫度，並從溶: 去除剩餘的氣態物質。在—種具體實施方式中，賴的端帽材料 2比處理室的石英管冷卻更快的材料製成。結果，姐爐中朝著 端巾目（更低咖度）產生氣流，導致殘餘物沉積在端帽上。在一種 實％方式中’用真线送機去除氣態物質。可在圖5巾的溫度分 佈中示出上述溫度序列。 又刀 ^在步驟422之後，執行最終的清潔處理以去除沉積在溶爐端 中目上的各種殘餘物。根據條件，可以通過簡單地顧端帽、刮擦、 I光、和/或其他方絲去_餘物。應該理解，清潔可從溶爐上 輕鬆去除的端清潔處理室_部方便得多。 根據所期望的最終產品，也可以執行其他的步驟。例如，如 果，望CIS或CIGS類型的薄膜太陽能電池，那麼提供額外的處理 1 乂提供另外的結構，例如透明材料層，例如覆蓋dS層的卻。 還應理解’本文伙述的實關和實财式制於示意性目 的’並且對本領域的技術人員來說存在據此進行的各種修改或變 化的暗示，這些修改或變化將包括在本帽的精神和範圍以及所 201123314 附申請專利範圍内。 圖5和圖5A是根據本發_—種實施方式的频的溫度分佈 的簡圖。這些圖僅是-個實關，其在本文林應限射請專利 範圍。溫度分絲-步詳細制了上述方法的概要（圖4)和說明 書中的溫度坡度變化處理。提供最佳的溫度分佈（圖5和圖认） 以舉例說雜據本發_—種實财式的域纽。此最佳分佈 調節處理室，爾止_度和大基板在高溫時_曲。如果溫度 攸升得過高過快’那麼可能會由於玻璃的軟化而出聽曲或損 壞。另外’考慮基板可用_雜量來確定熱能_量，並保持 玻璃基板_勻性和結構完整性。例如，通過在多個步驟中週期 ! 生地控制加熱處理的溫度，使基板保持—定水準的财和鬆弛 (relaxing)並保持必需的結構完整性。如上文所說明的，材料（例 如玻璃）趨向於在48代或更高的溫度時變形，因此，要小心避 免L長基板暴路於南溫的時間。參相5，在用包括砸化物物質和 載氣的氣態物質保械理魏境的_，將？個基板放到炫爐 中。在一種實施方式中，在將氣態物質填充人處理室之前抽出處 理至内的空氣。在一種示例性實施方式中，載氣包含I氣。例如， 氣態物質將處理室填充域⑽托的壓力。將多個基板相對於重 力方向垂直定向而設置，用數字N限定多個基板，其中N大於5。 在種實施方式中，基板包括玻璃基板，例如納約玻璃。炫爐處 於低於1GG c的第—溫度。然後，雜爐加熱至溫度範圍為約 350X到45〇〇C的第二溫度。 、、 15 201123314 在熱處理間隔中’將第二溫度保持在350〇C至45〇。(：之間約 10至60分鐘（時間段）。玻璃基板的尺寸可以是，但不限於， cmxl65 cm。處理這樣的大基板的一個挑戰是基板在高溫時的翹 曲。如果使溫度直接升至T3，就會出現翹曲或損壞。如所示出的， 校準從T2爬升至T3的斜率，以減小和/或消除損壞基板的風險。 在一種實施方式中，如圖5A所示，當溫度從T2爬升至T3時， 去除部分砸化物氣體。通過將處理室中的溫度保持在Τ2 一段時 間，使基板鬆弛並穩定。根據從每個基板上的銅和銦複合結構至 少初始地形成銅銦二硒化物膜的目的，設置此間隔時的保持時間。 然後’將熔爐冷卻至從5〇〇0C至室溫範圍的第三溫度。在石西 化處理的過程中，殘餘的硒化物物質會聚集在之前在圖3中示出 的内部處理區域320中。在高溫下，硒化物物質在内部處理區域 320内保持蒸氣形式。隨著溫度降低，硒化物物質沉積在更冷的表 面上。在一種優選實施方式中，沒有隔絕的金屬端帽3〇4由於具 有更高的熱導率而比石英處理室3〇2冷卻得快得多。產生溫度梯 度’這在内部處理區域32〇内產生對流。對流導致元素硒朝著端 帽304流動’並沉積在更冷的端帽區域322上。通過此方法，通 過使處理區域的内部區域的殘餘硒化物物質分解，可使内部處理 區域320保持為基本沒有元素砸物質。201123314 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to photovoltaic technology. More specifically, the present invention provides a use of a copper indium diselenide material (or indium copper selenide, CIS), a copper-faced bismuth telluride material (or copper indium gallium selenide 'CIGS), and/or other Method and structure of a thin film photovoltaic device of matter. The invention can be applied to photovoltaic modules, flexible sheets, glass for buildings or windows, automobiles, and the like. [Prior Art] In the process of manufacturing a film of the CIS and/or CIGS type, there are various manufacturing problems, for example, maintaining the structural integrity of the substrate material, ensuring the uniformity and fineness of the film material, and the like. While some of these problems have been solved by past traditional techniques, they are often insufficient in many cases. Among other things, systems used to make as and/or CIGS films (eg, processing chambers) are often difficult to clean. Accordingly, improved systems and methods for fabricating thin film photovoltaic devices are desired. SUMMARY OF THE INVENTION The present invention generally relates to photovoltaic technology. More specifically, the present invention provides a method and structure for a thin film photovoltaic device using copper indium diselenide material (CIS), copper indium gallium diselenide material (CIGS), and/or other materials. The present invention is applicable to photovoltaic modules, flexible sheets, glass for buildings or windows, automobiles, and the like. According to one embodiment, the present invention provides a method of manufacturing a copper indium diselenide semiconductor film using a self-cleaning furnace. The method includes transferring a plurality of substrates into a furnace, the furnace including a processing region and at least one end cap region detachably coupled to the processing region, the plurality of substrates being vertically oriented with respect to a direction of gravity, using a number N A plurality of substrates are defined, wherein N is greater than 5, and each substrate has a copper and indium composite structure. The method further includes introducing a gaseous substance including a hydrogen species and a selenide species and a carrier gas into the furnace, and transferring the thermal energy into the furnace to raise the temperature from the first temperature 201123314, and the second temperature 'the second temperature range is From about Μ. . . To about. . Therefore, at least the indium composite film of the indium and tantalum is formed on each of the substrates. The method further comprises the step of causing the lion's body substance 2 in the inner region of the dragon's domain. The method further includes an elemental selenide species in the end cap region operable at the third temperature. Moreover, the method includes 'resolving the residual telluride material' from at least the (four) region of the field of view to maintain the inner region substantially free of elemental stone-west material. In a specific embodiment, when the hydrogen gas in the _ middle (four) boots is about 4GG ° C or higher, the hydrogen halide gas is thermally activated to cause:, solution, formation of read 砸 (Se) or code. Cluster (Se2 or Se3). The end cap region includes a lid that is cooled by water and heated by a lamp to control the temperature of the lid. The degree of monitoring = is kept cool for use as a ''low temperature fruit') so that the sputum f (7C sputum and supplement) can be deposited on the lid and inhibit the reaction between hydrazine and other membrane materials such as steel. After completing the one or more processing loops, the cover of the end cap region can be further cleaned with a cloth (eg, material) to remove the deposit_residue 1 . The present invention provides many benefits over conventional techniques. Mao Ming's money and method are age-matched, _ in various embodiments, the residual gas is incorporated into the ^^. It can be easily cleaned. In addition, it has other special fields. The present invention relates generally to photovoltaic technology, and more particularly to methods and structures for the use of copper indium dimer matter (CIS), copper indium gallium nitride (s), and/or other thin film photovoltaic devices. , (^) group, flexible sheet, glass for building or window, automobile, etc. Applied to photovoltaic pattern ^ is a simplified diagram of a transparent 201123314 substrate with overlapping electrode layers in accordance with an embodiment of the present invention. Is an embodiment, in It is not intended to limit the scope of the claims. As shown, the structure 100 comprises a transparent substrate 1 .4 In one embodiment, the substrate 104 may be a glass substrate, such as a sodium dance glass. However, other types may also be used. Substrate. Examples of the substrate include borosilicate glass, acrylic glass, sugar glass, specialty ComingTM glass, etc. As shown, a contact layer comprising a metal electrode layer 102 is deposited on the substrate 1〇4. According to one embodiment, The metal electrode layer 102 includes a metal material characterized by having a predetermined conductivity based on a solar cell application film. The metal electrode layer 102 can be deposited in four ways according to the condition of the fourth electrode. For example, the metal electrode layer 102 mainly includes sputtering. The deposited molybdenum film is emitted. For example, the thickness may range from 200 to 700 nm. A thin film of material may be deposited on the substrate using a sputtering apparatus (for example, a DC magnetron sputtering apparatus). Such a device is well known. And is commercially available. However, it should be understood that other types of devices and/or methods may be used, for example, in a vacuum based ring. Evaporation. As an example, a sputter deposition method is described below. ' Sputter deposition is by sputtering or ejecting a material from a "target (target), or source, and then depositing it on a substrate (eg, a germanium wafer or glass) A physical vapor deposition (PVD) method for depositing thin films. The sputtered atoms ejected from the target have a broad energy distribution, typically up to a few 10 eV (100,000 κ). By varying the background air pressure, the entire range from high energy ballistic impact to low energy thermal motion can be obtained. The sputtering gas is typically an inert gas such as argon. In order to effectively perform the momentum transfer, the atomic weight of the sputtering gas should be close to the atomic weight of the target, and therefore, ruthenium is preferred for sputtering light elements, and helium or gas is used for heavy elements. Reactive gases can also be used to fluorinate the compound. According to the i art parameter, a compound can be formed on the silk surface, on a flying towel or on a substrate. The availability of many of the parameters controlling sputter deposition makes it a complex process, but also allows the skilled artisan to control the growth and microstructure of the crucible to a large extent. 6 201123314 Figure 2 is a simplified diagram of a composite structure comprising copper and indium materials in accordance with an embodiment of the present invention. This figure is only an example and should not limit the scope of the claims herein. In this embodiment, the structure 2 includes a glass substrate 2, 8, preferably a glass, having a thickness of about 1 to 3 mm. For example, the glass substrate 2〇8 serves as a support layer. A metal layer is deposited on the substrate. For example, the metal layer is applied as a metal layer to supply contact. For example, layer 206 primarily comprises a lava that has been deposited through the filaments, with a j degree of 200 to 700 nm. In a specific embodiment, the initial chromium film is accumulated on the glass. For example, a chrome layer is provided to ensure good adhesion of the entire structure to the substrate 208. Other types of materials can also be used in the _ layer, such as sulphur dioxide, smashing, and the like. Layers 204 and 202 primarily comprise a copper layer and an indium layer deposited on top by a sputtering process. As shown in FIG. 2, the indium layer covers the copper layer. However, it should be understood that ^ can be used in other arrangements. In another embodiment, the copper layer covers the indium layer. As an example, a miscellaneous (e.g., a DC magnetron sputtering device) is used to deposit a film of a material (e.g., layer 2, 2, and/or application). It should be understood that a sputtering device of the type can be used. Such devices are well known and commercially available. His materials. It should be understood that the technique of bribes throughout the application is two <RTIgt;<>> and other types of equipment and/or methods may be used, for example, to deposit copper and indium materials in a vacuum based environment. In some implementations: in addition to copper and steel materials, deposited materials can be formed ^ 〇 9 = according to the embodiment, the ratio of copper to indium materials is less than κ = 〇 · 96) 'that is, each indium material Less than one piece of copper. For an embodiment, the structure is formed by processing structure 100. For example, Cu and Ιn are deposited to form structure 20G. As described above, in the application mode, the (f)n complex or the Cu/In combination is formed during the process of the Cu film and the In film treatment: Fig.: 201123314 The technology described in the entire text is accessible to the lion, and (4). u This vacuum is evaporated to deposit copper and indium in a manner other than the copper and indium materials of gallium material (not shown in Figure 2).乂心成,儿积疋 A simplified diagram of the composite structure including copper and indium composite films according to the present invention (4). This figure is only an example, which is not shown herein. The structure 210 includes a transparent substrate 216: a back contact). For example, layer 214 primarily comprises a battered film deposited by sputtering. In a specific embodiment, an initial chromium film is deposited on the glass 216 prior to the sinking material to provide a good texture of the entire structure to the substrate 21〇. Layer M2 mainly includes copper indium alloy or fine composite (four). For example, fine mixing or alloying results in improved uniformity or advantageous morphology of the composite copper indium film. This modified structure is loaded into the desired CIS film after the Wei step. According to one embodiment, a copper indium alloy material is formed from separate layers of copper and indium materials that diffuse into each other. For example, the treatment of forming a fine alloy material can be promoted by subjecting the structure to high temperatures. 3 is a simplified diagram of a furnace in accordance with an embodiment of the present invention. This figure is only an embodiment, which should not limit the scope of the patent application herein. As shown, the furnace 300 includes a process chamber 302 and an end cap 3〇4 of the chamber. According to one embodiment, the reaction chamber 302 is characterized by a volume greater than 2 liters. The inner surface and the space area of the process chamber 3〇2 are described as the inner processing area 32〇. In one embodiment, the processing chamber 302 can include a quartz tube. End cap region 322 represents the inner surface of end cap 3〇4 and the surface adjacent the tube that is partially exposed to inner processing region 320. In one embodiment, the end cap 304 can be made of a metallic material. In certain embodiments, end caps 3〇4 and 8201123314" different surface reactivity, thermal conductivity, secret, and/or L of various types of materials may be deposited in the end cap 304 chamber to be torn to the sample or The feeder to be loaded on the substrate of the chamber #, the air pump frequency package (four) the age sub-pump (10) and the ί-turn pump to the line to send the machine can be increased (four) and dry pump combination, the main gas; If required for special application and/or processing, it may be introduced into the process chamber 3〇2 via a gas turbulent gas and a domain dilution gas (for example, helium, nitrogen, argon = or milk). 31() is evacuated via the rotary pump 312 = to 302, and the rotary pump 312 has no dedicated partition in the manifold through the gate valve and the conduction chamber 318 and the manifold training chamber 30. In the reaction furnace, in the reaction to The externally mounted heating element 3❶6 of 02 can be used in many applications. According to one embodiment, thermal energy is applied by a substrate of a miscellaneous 300 _ ^ surface type and is used for 51 various types of gaseous matter. In an embodiment Positioning one or more glass plates or substrates vertically near the center of the chamber. As an example The substrate 3() 8 may be similar to that described in FIGS. 2 and 2A (for example, a germanium or complex = Cu/In layer covering the metal on the substrate). In the case of a gas containing germanium (for example, in the presence) These layers are placed in the processing chamber. After annealing the material for a given period of time, 'copper, indium, and then diffuse and react to form a high quality copper indium dimuide (CIS) film. It is a simplified diagram of the invention for forming a copper indium diselenide layer according to an embodiment of the present invention. This figure is only an example, which should not limit the scope of the claims herein. Many other variations, modifications, and adaptations will be recognized. It should also be understood that the embodiments and implementations described herein are only used for illustrative purposes with 201123314, and it is suggested to those skilled in the art that Various modifications and changes are intended to be included within the scope of the method and the scope of the accompanying claims. As shown in Figure 4, the method can be briefly summarized below: 1. Start; 2. Provide multiple With copper and indium complex a substrate of the structure; 3. introducing a gaseous substance including a hydrogen substance and a selenium substance and a carrier gas into the furnace; 4. transferring the heat energy into the furnace to raise the temperature from the first temperature to the second temperature. Maintaining at a second temperature for a period of time; 6. decomposing any residual selenide species in the interior region of the processing zone of the furnace; 7. reducing the temperature to a third temperature; 8. maintaining the temperature at about a third temperature for a period of time 9. deposit element code material in the vicinity of the end cap region that can be operated at the second temperature; 10. reduce the temperature from the third temperature gradient to approximately the first temperature; 11. remove the gas; and 12. stop. The steps are only examples and should not limit the scope of the invention. Many other variations, modifications, and alternatives will be apparent to those of ordinary skill in the art. For example, the various steps outlined above may be added, removed, modified, rearranged, repeated, and/or overlapped as contemplated within the scope of the invention. As shown, method 4 begins with start step 402. Here, the user of the method begins with a processing chamber such as those mentioned above, as well as other steps. The chamber 201123314 can be maintained at approximately room temperature prior to implementation of the method. - Step 402 is to transfer a plurality of substrates into the processing chamber. The parent of the plurality of substrates may be disposed to be oriented perpendicular to gravity. A plurality of substrates may be defined by a number N, where N is greater than five. The plurality of substrates may include five or more separate substrates. In another embodiment, the plurality of substrates may comprise 40 or more separate substrates. For example, the size of each substrate may be about 65 _65 coffee. Each substrate is held in a substantially flat _ structure with no warpage. For example, if the substrate is placed in a direction other than the direction perpendicular to gravity, gravity will cause warpage under the substrate. This situation occurs when the substrate (4) reaches the operating temperature and jeopardizes the structural integrity of the substrate. Typically, the glass substrate, especially the nano-vessel substrate, is in use. (: (commonly referred to as strain point) begins to soften. In an embodiment, the substrates are also isolated from each other according to a predetermined interval to ensure uniform reaction with the gaseous species to be introduced into the furnace. After the processing chamber, a gaseous substance (including a hydrogen species, a code material, and/or a carrier gas) is introduced into the processing chamber at step +. In one embodiment, the gas matrix contains at least a coded material (eg, H2Se) In the other way, the gaseous substance includes other types of chemically inert gases, such as helium, milk, etc. For example, the substrate is placed in a gas containing helium (for example, H2Se). Then in step 4. 〇8, the furnace is heated to a temperature ranging from about 乂 to 450 〇 C. In order to heat the processing chamber, heat transfer can be achieved by adding or subtracting parts, heating coils, etc. For example, in the step of the step, At least the formation of a copper-indium two-boot film by the reaction of a gaseous substance with a composite (or layered) structure of copper and indium on each substrate begins. In a specific embodiment, the copper and indium materials are separated. Floor Dispersing into each other to form a single layer of copper indium alloy material. In the second step of the heat treatment interval, the second temperature is maintained between 3 and 4 for about 60 minutes (time period). In another embodiment, the second temperature can range from 390 〇C to 410 〇C. For example, the time period provided by step 41 用于 for maintaining the temperature enables the formation of ass. As the temperature increases, the internal pressure will also increase. In a specific embodiment, the pressure inside the pressure release-dosing is maintained at about 650 Torr. In an embodiment, during the temperature ramping from the first temperature to the second temperature and the second temperature is stabilized, the hydrogen purchase is partially thermally cracked into helium atoms and Se vapors. Se strips can be removed partially in one or more sections. For example, a low temperature | can be installed to extract & vapor directly from the chamber card. In addition, the implementation of the 'cooling' cap can be used to absorb or condense the vapor or Se cluster carried by the convection from the hot chamber interior to the cooling_cap region to effectively extract the selenium material. During the temperature maintenance (step 41A), in step 412, additional removal of the residual material is begun. In step 414, a vacuum is created in the processing chamber by vacuum. In a specific embodiment, the residual de-mass removal process can be performed. (d) The process chamber as suggested in the above paragraph is in a vacuum configuration. At step 416, a vacuum is generated in the processing chamber (step 414), and hydrogen sulfide (H2S) species is introduced. The secret of the second temperature stability level leads to a reaction with the texture containing the indium complex. For example, the following reaction occurs in 201123314, CUInSe2 + H2S - CuInSexS| x+, which removes Se' from the film on the substrate and regenerates in the environment within the chamber. At the same time, it can be continuously transported from the thermal reaction chamber to the female including the end zone mosquito-cooled area, or the "grain" can be accumulated on the surface of the end cap, keeping the reaction chamber substantially free of elements. The gas environment in the furnace is modified such that the vaporized material is removed and the hydrogen sulfide material is introduced to 'start the second temperature rise treatment, step 418. In a specific embodiment, the nitrogen and the boots function as a carrier gas. The substance is introduced. The temperature of the furnace is raised to a third temperature ranging from about 5 〇〇 QC to 525 。 For example, the third temperature is calibrated in order to cause a reaction between the hydrogen hydride material in the furnace and the substrate. In a preferred embodiment, the metal end cap 304 is cooled much faster than the quartz processing chamber due to the higher thermal conductivity of the metal end cap. Even when the chamber tube plus 2 is hot, the metal end cap 3〇4 can also remain “cooled, (basically under 2〇〇〇c). A temperature gradient is generated' which creates convection within the internal processing region 32(). As a result, the code and/or other residual material is deposited in the end red. In the frequency-frequency embodiment, the furnace 3 (10) as described above has a separately controllable heating unit for maintaining temperature uniformity within the furnace. For example, these heaters can also create a temperature differential that causes the reference/other residue to the end cap region. The temperature is maintained at the third temperature for a certain period of time at step 420' until the formation of the CIS layer is completed. According to the purpose of extracting one or more kinds of stone materials from the copper indium dimuthide film, the retention time of the environmental towel placed on the sulphur-containing material at the time of separation is set. It is beneficial to remove a predetermined amount of impurities. In a specific embodiment, about 5% _ is removed from the membrane and replaced with about 5% sulfur. According to one embodiment, 201123314, it is desirable to carry out a complete reaction between the ruthenium material and the CIS membrane. In step 422, the controllable temperature ramp down process begins at the removal of the butterfly money. In the step, the cold portion of the furnace is cooled to a first temperature of about room temperature, and the remaining chaotic material is removed from the furnace. For example, the gaseous material is removed by a vacuum pump. The above temperature sequence can be shown in the graph $(five) degree distribution. After the decomposition of the residual stone-thin material, the gradual gradient reduction treatment is started. (d) The furnace is cooled to a temperature of about room temperature and dissolved: the remaining gaseous material is removed. In a specific embodiment, the end cap material 2 is made of a material that cools faster than the quartz tube of the processing chamber. As a result, airflow is generated in the furnace toward the endoscope (lower calorie), causing residue to deposit on the end cap. In a real-world mode, the gaseous substance is removed by a machine. The above temperature sequence can be shown in the temperature distribution of the Figure 5 towel. Further, after step 422, a final cleaning process is performed to remove various residues deposited on the furnace end. Depending on the conditions, it is possible to simply remove the residue by means of an end cap, a scratch, an I-light, and/or other square wires. It should be understood that it is much more convenient to clean the end cleaning chamber that can be easily removed from the furnace. Other steps can also be performed depending on the desired end product. For example, if a thin film solar cell of the CIS or CIGS type is desired, then additional processing is provided to provide additional structures, such as a layer of transparent material, such as a layer covering the dS. It should also be understood that 'the context of the subject matter and the stipulations of the present invention are for illustrative purposes' and that there is a suggestion to those skilled in the art that various modifications or changes may be made thereto, and such modifications or variations will be included in the cap. Spirit and scope as well as the scope of the patent application of 201123314. Fig. 5 and Fig. 5A are diagrams showing the temperature distribution of the frequency according to the embodiment of the present invention. These figures are only a real one, and in this article, Lin should limit the scope of patents. The temperature splitting step is a detailed description of the above method (Fig. 4) and the temperature gradient change process in the specification. Provide the best temperature distribution (Figure 5 and figure recognition) to exemplify the hybrid field of the present invention. This optimal distribution adjusts the processing chamber, _ degrees and large substrates at high temperatures. If the temperature rises too high and too fast, then it may be heard or damaged due to the softening of the glass. In addition, it is considered that the substrate can be used to determine the amount of thermal energy and maintain the glass substrate _ uniformity and structural integrity. For example, by controlling the temperature of the heat treatment in a plurality of steps, the substrate is maintained at a constant level of concentration and relaxation and maintains the necessary structural integrity. As explained above, materials such as glass tend to deform at temperatures of 48 generations or higher, so care must be taken to avoid the long path of the L-long substrate during the south temperature. In phase 5, in the use of gaseous substances including bismuth compounds and carrier gases, the _, will be? The substrates are placed in a bright furnace. In one embodiment, the air treated to the interior is withdrawn prior to filling the gaseous material with the human processing chamber. In an exemplary embodiment, the carrier gas comprises I gas. For example, the gaseous material will fill the pressure in the processing chamber filling zone (10). A plurality of substrates are vertically oriented with respect to the direction of gravity, and a plurality of substrates are defined by a number N, where N is greater than five. In an embodiment, the substrate comprises a glass substrate, such as a nanoglass. The blaze is at a temperature below 1 GG c. The furnace is then heated to a second temperature in the range of about 350X to 45 °C. , 15 201123314 Maintain the second temperature at 350 ° C to 45 在 in the heat treatment interval. (: about 10 to 60 minutes (time period). The size of the glass substrate can be, but is not limited to, cmxl65 cm. One challenge in handling such a large substrate is the warpage of the substrate at high temperatures. If the temperature is raised directly Warping or damage may occur to T3. As shown, the slope from T2 to T3 is calibrated to reduce and/or eliminate the risk of damage to the substrate. In one embodiment, as shown in Figure 5A, Part of the telluride gas is removed as the temperature climbs from T2 to T3. The substrate is relaxed and stabilized by maintaining the temperature in the process chamber for a period of time 2. At least initially formed from the copper and indium composite structures from each substrate. The purpose of the copper indium diselenide film is to set the hold time at this interval. Then 'cool the furnace to a third temperature ranging from 5 〇〇 0 C to room temperature. During the lithification process, residual selenide material It will accumulate in the internal processing zone 320 previously shown in Figure 3. At high temperatures, the selenide species remains in vapor form within the internal processing zone 320. As the temperature decreases, the selenide species deposits in the colder On the surface, in a preferred embodiment, the uninsulated metal end cap 3〇4 cools much faster than the quartz processing chamber 3〇2 due to the higher thermal conductivity. A temperature gradient is generated 'this is in the internal processing area Convection occurs within 32 Torr. Convection causes elemental selenium to flow toward the end cap 304 and deposits on the cooler end cap region 322. By this method, the internal selenide species in the inner region of the treated region can be decomposed to internalize Processing zone 320 remains substantially free of elemental cerium species.
在已經改變炼爐中的環境使得任何殘餘的石西化物物質被分解 並且沉積在端帽區域322處之後，根據在基板的表面上形成as 層的處理，可引入另外的步驟。在另一實施方式中，在形成CIS 16 201123314 以防止基板輕曲 膜時，可使用另外的溫度坡度變化和保持步驟 或變得損壞。 在形成CIS層之後，開始進行溫度坡度下降處理，然後將炼 爐冷卻至大約室溫的第-溫度。_—種實施方式，具體地校準 冷卻處理。此纽的結果是，銅、銦和祕此·並發生反應， 以形成高品質的銅銦二喊膜。在—種實施方式中，在冷卻處理 的過程中，使用諸如氮氣的氣態物質。 圖6A是根據本發明的一種實施方式的薄膜銅銦二硒化物器 件的簡圖。此圖僅是—個實例，其在本文巾不應限射請專利範 圍。如所示出的，在玻璃基板610上支撐結構6〇〇。根據一種實施 方式，玻璃基板包括鈉鈣玻璃，其厚度為約丨至3111111。在基板61〇 上沉積包括金屬層608的後觸點（backcontact)。根據一種實施方 式，層608主要包括通過濺射而沉積的鉬膜。結構6⑽的第一有 源區包括半導體層606。在一種實施方式中，半導體層包括p型銅 銦二砸化物（CIS)材料，該材料的特徵在於其整體厚度為5〇〇至 1500 μπι。應該理解，其他半導體層可以包括其他類型的材料，例 如CIGS。結構600的第二有源部分包括η型半導體材料的層6〇4 和602 ’例如CdS或ΖηΟ。圖6Α示出了包括具有不同電阻係數水 準的兩個CdS層602和604的結構600的第二有源部分。圖6Β 中示出了另一實施方式，其尹，該結構的第二有源部分包括cds 層和ΖηΟ層。 圖6Β是根據本發明的另一實施方式的薄膜銅銦二硒化物器 201123314 件的簡圖。此圖僅是一個實例，在本文中其不應限制申請專利範 圍。如所示出的，結構620支撐於玻璃基板63〇上。根據—種^ 施方式，玻璃基板包括鈉鈣玻璃，其厚度約為丨至3爪爪。在美板 630上沉積包括金屬層628的後觸點。根據一種實施方式，層似$ 主要包括通過濺射而沉積的鉬膜。結構62〇的第一有源區包括半 導體層626。在-種實施方式十，半導體層包括p型鋼鋼二:化物 (CIS)材料。應該理解，其他半導體層可以包括其他類型的材料， 例如CIGS。結構62〇的第二有源部分包括n型轉體材料的層After the environment in the refining furnace has been changed such that any residual lithiated material is decomposed and deposited at the end cap region 322, an additional step can be introduced depending on the treatment of forming the as layer on the surface of the substrate. In another embodiment, additional temperature ramp changes and retention steps may be used or become damaged when forming CIS 16 201123314 to prevent the substrate from being filmed. After the formation of the CIS layer, the temperature gradient reduction process is started, and then the furnace is cooled to a first temperature of about room temperature. _ - an embodiment, specifically calibrating the cooling process. As a result of this New Zealand, copper, indium, and the like reacted to form a high-quality copper-indium yoke film. In one embodiment, a gaseous species such as nitrogen is used during the cooling process. Figure 6A is a simplified diagram of a thin film copper indium diselenide device in accordance with one embodiment of the present invention. This figure is only an example, and it should not be limited to the patent scope. As shown, the structure 6 is supported on a glass substrate 610. According to one embodiment, the glass substrate comprises soda lime glass having a thickness of from about 丨 to 3111111. A back contact including a metal layer 608 is deposited on the substrate 61A. According to one embodiment, layer 608 primarily comprises a molybdenum film deposited by sputtering. The first active region of structure 6 (10) includes a semiconductor layer 606. In one embodiment, the semiconductor layer comprises a p-type copper indium di- telluride (CIS) material characterized by an overall thickness of 5 Å to 1500 μm. It should be understood that other semiconductor layers may include other types of materials, such as CIGS. The second active portion of structure 600 includes layers 6〇4 and 602' of an n-type semiconductor material such as CdS or ΖnΟ. Figure 6A shows a second active portion of structure 600 comprising two CdS layers 602 and 604 having different levels of resistivity. Another embodiment is shown in Figure 6A, the second active portion of the structure comprising a cds layer and a Ζn layer. 6A is a schematic diagram of a thin film copper indium diselenide device 201123314 according to another embodiment of the present invention. This figure is only an example and should not limit the scope of the patent application herein. As shown, the structure 620 is supported on a glass substrate 63. According to one embodiment, the glass substrate comprises soda lime glass having a thickness of about 丨 to 3 claws. A back contact comprising a metal layer 628 is deposited on the sheet 630. According to one embodiment, the layer consists essentially of a molybdenum film deposited by sputtering. The first active region of structure 62A includes a semiconductor layer 626. In a tenth embodiment, the semiconductor layer comprises a p-type steel two-component (CIS) material. It should be understood that other semiconductor layers may include other types of materials, such as CIGS. The second active portion of the structure 62A includes a layer of n-type swivel material
CdS 624 和 ΖηΟ 622。 將光伏電池或太陽能電池（例如，上述裝置6〇〇)構造為大面 積Ρ-η結。當太陽光中的光子撞擊光伏電池時，光子會被反射而穿 過透明電極層，或被吸收。半導體層吸收導致產生電子空穴對的 :里。光子需要具有比帶_能量更大的能量，以激勵電子從價 =進入導帶。這允許電子流過材料以產生電流。互補的正電荷或 空穴’在與絲電财的電子相_方向上流動。具有許多光伏 電池的太触電池板可將域轉化成直流電。 對於薄膜太陽能電池應用來說，基於銅銦二雜物（⑶）構 造的半導體由於其具有高光學吸㈣數和通㈣光電特性而尤其 二有吸引力。糊上，對於給定裝置巾的特定需要，可操作並調 :這些特性。魏夠使整個層具有更好的均勻性，並由此減少膜 的重錄置的數里’ ^有撕提高量子效率並由此提高轉換效 Ο 201123314 本發明提供在用於太陽能電池板的大玻璃基板上製造基於 as和/或基於CIGS的太陽能電池的方法。可將圖6中描述的器 件結構圖魏職《基板上的單獨的域能電池，並彼此連接 以形成太陽㈣池板。耻，本發明提供了—歸造薄膜太陽能 電池板的節省成本的方法。 應該理解’不細和銦蘭沉_序如何都㈣實現本發明 ，所有益處。也就是說，可首先沉積銦，或將臈作為夾入物或堆 疊的更薄的多個層而沉積。 _理解，本文巾描賴實施例和實财式·於示例性目 的’並且對於本賴技術人貞來說，存在據此進行的各種修改或 變化的暗示，這些修改或變化包括在本中請的精神和範圍以及所 附申請專利範圍内。 圖7疋根據本發明的一種實施方式的在硒化物物質的分解之 前的自清魏__。此®僅是-個實例，其在本文中不應限 制申睛專利範圍。如所示出的，雜7⑽包括處理室7〇2和室的 端巾目*704。將處理室7()2的内表面和空間區域描述為内部處理區域 706。在—種實施方式中，處理室7〇2可包括石英管。端帽區域观 ^表暴路於内部處理區域706的端帽704的内表面。如上所述， 端f目7〇4和處理室702的特徵在於表面反應性和/或對於各種類型 、冬二物質的粘性不同。例如，在某一條件下，各種類型的材料 可月匕’儿積在端帽7〇4上，但是不沉積在腔室7❶2的内表面上。在 種具體實施方式中，端帽區域7〇2由具有比處理室7〇2低的比 19 201123314 熱的材料製成。在一種實施方式中，端帽704至少由金屬材料組 成。在硒化處理的過程中，殘餘的硒化物710可能沉積在内部處 理區域706中。根據一種實施方式，可通過在内部處理區域和端 帽區域之間引入機械擋板來形成溫度梯度，使得對流能夠將殘餘 物從内部處理區域帶走，並防止殘餘的硒化物71〇沉積在内部處 理區域706中。 還應理解，本文中描述的實施例和實施方式僅用於示例性目 的，並且對於本領域技術人員來說，存在據此進行的各種修改或 變化的暗示，這些修改或變化包括在本申請的精神和範圍以及所 附申請專利範圍内。 圖8A是根據本發明的一種實施方式的在硒化物物質的分解 之月1j的自清潔溶爐的簡圖。此圖僅是一個實例，其在本文中不應 限制申請專利範圍。如所示出的，熔爐8〇〇包括處理室8〇2和室 的端帽804。將處理室802的内表面和空間區域描料内部處理區 域806。在-種實施方式中，處理室8〇2可包括石英管。端帽區域 8〇8代表暴露於内部處理區域806的端帽8〇4的内表面。在一種實 施方式中’端帽804可由金屬材料製成。在碼化處理的過程中， 殘餘的硒化物810可已經沉積在内部處理區域8〇6中。根據一種 實施方式，可通過在内部處理區域806和端帽區域8〇8之間引入 機械擋板來形成溫度梯度，使制流關將殘餘麵從内部處理 區域帶走’縣本上防止錄_化物⑽崎在⑽處理區域 806 中0 20 201123314 圖8B是根據本發明的一種實施方式的在硒化物物質的分解 和70素硒在端帽處的沉積的過程中的自清潔熔爐的簡圖。此圖僅 是一個實例，其在本文中不應限制申請專利範圍。如所示出的， 熔爐820包括處理室822和室的端帽824。將處理室822的内表面 和空間區域描述為内部處理區域826。在一種實施方式中’處理室 822可包括石英管。端帽區域828代表暴露於内部處理區域耵6 的端帽824的内表面。在一種實施方式中，端帽824可由金屬材 料製成。在硒化物物質的分解過程中，包括元素硒的殘餘物質83〇 被蒸發，並（由熱梯度所導致的對流攜帶）從内部處理區域826 朝著端帽區域824流動。 圖8C是根據本發明的一種實施方式的在硒化物物質分解和 兀素硒在端帽處沉積之後的自清潔熔爐的簡圖。此圖僅是一個實 Π /、在本文中不應限制申凊專利範圍。如所示出的，溶爐840 包括處理室842和室的端帽844。將處理室842的内表面和空間區 域描述為内部處理區域846。在一種實施方式中’處理室8耵可包 括石英官。端帽區域848代表暴露於内部處理區域846的端帽844 的内表面。在一種實施方式中，端帽844可由金屬材料製成。在 硒化物物質的分解和沉積之後，殘餘的硒化物85〇包含在端帽區 域848中。例如，由於端帽和處理室之間的溫度梯度，至少部分 也由對•導致殘餘砸化物81G的沉積或冷凝。通過增加用作可押 可滲透屏障的擋板結構’可使溫度梯度大幅增強。在完成CIS層 的形成並從處理室842去除基板之後，可用布（例如，亞麻布， 201123314 =2=)機械地清除殘餘的靴物。應理解，通過使砸化 物和/或其_餘㈣綠端舰構上，可使清轉 =易地擦去端帽結構上的殘餘物。而在各種常規技術中，從溶 爐>月除殘餘物通常需要清潔處理室的内部。 圖=、圖8B和圖8C是殘餘的石西化物的分解和當元素石西沉積 理至的端帽區域處時的路徑的步驟的簡圖。 還應理解，本文中描述的實例和實施方式僅用於示例性目 ^，並且對於本賴技術人M來說，存她b進行的各種修改或 變化的暗示’這些修改或變化包括在本申請的精神和範圍以及所 附申請專利範圍内。 圖9是根據本發明的一種實施方式的在砸化物物質分解和元 素石西在端帽處沉積之後的自清潔賴的咖。此關是一個實 例，其在本文中不應限制申請專利範圍。如所示出的，溶爐则 包括處理t 902和室的端帽904。將處理室9〇2的内表面和空間區 域描述為内部處理區域906。在一種實施方式中’處理室9〇2可包 括石英管。端帽區域908代表暴露于内部處理區域9〇6的端帽9〇4 的内表面。在一種實施方式中’端帽剛可由金屬材料製成。在 碼化物物質分解和沉積之後，殘餘_化物9W包含在端帽區域 908中。在完成CIS層的形成並從處理室902去除基板之後，可以 使用布（例如亞麻布，或類似的材料）來機械地清除殘餘的石西化 物。 還應理解’本文中描述的實施例和實施方式僅用於示意性目 22 201123314 的’並且暗示了本躺的顯人㈣以觀妨的各種修改或變 化’這些修改或變化㈣包括在本中請的精姊範圍以及所附申 請專利範圍内。雖然上文中已經主要描述了用於cis和域 薄膜電池的特定結構，但是，在不_由本文申請專利範圍所描 述的發明的前提下，也可錢其他特定的as切或aGs構造， 例如，那些在已授權的美國專利第4,611，〇91號和第4,612,411號 中提到的，其結合於此以供參考。 【圖式簡單說明】 < 圖1是根據本發明的一種實施方式的具有重疊電極層的透明 基板的簡圖； 圖2疋根據本發明的一種實施方式的包括銅和姻膜的複合結構 的簡圖； 圖2A是根據本發明的一種實施方式的包括銅銦複合物/合金的 複合結構的簡圖； 圖3是根據本發明的一種實施方式的熔爐的簡圖； 圖4是根據本發明的一種實施方式的用於形成銅銦二硒化物層 的過程的簡圖； 圖5和圖5A是根據本發明的一種實施方式的熔爐的溫度分佈 的簡圖； 圖6A是根據本發明的一種實施方式的薄膜銅銦二硒化物器件 的簡圖； 圖6B是根據本發明的另一實施方式的薄膜銅銦二硒化物器件 23 201123314 的簡圖； 圖7是根據本發明的一種實施方式的在硒化物物質的分解之前 的自清潔炼爐的簡圖； 圖8A是根據本發明的一種實施方式的在硒化物物質的分解之 前的自清潔溶爐的簡圖； 圖8B是根據本發明的一種實施方式的在硒化物物質的分解和 元素硒在端帽處的沉積的過程中的自清潔熔爐的簡圖； 圖8C是根據本發明的一種實施方式的在硒化物物質的分解和 元素硒在端帽處的沉積之後的自清潔熔爐的簡圖； 圖9是根據本發明的一種實施方式的在硒化物物質的分解和元 素砸在端帽處的沉積之後的自清潔溶爐的簡圖。 【主要元件符號說明】 100處理結構、結構 102金屬電極層 104透明基板、基板 200結構 202層 204層 206沉積金屬層、金屬層、層 208玻璃、玻璃基板、基板 210複合結構、結構、基板 212層 214金屬電極層、層 216透明基板、玻璃、基板 300熔爐 24 201123314 302處理室 304端帽 306加熱元件 308基板 310渦輪分子泵 312 旋轉泵 314 注氣管道 316 歧管 318 傳導閥 400 方法 402 步驟 404 步驟 406 步驟 408 步驟 410 步驟 412 步驟 414 步驟 416 步驟 418 步驟 420 步驟 422 步驟 424 步驟 426 步驟 428 步驟 600支撐結構 602層 604層 606半導體層 608金屬層 610基板 201123314 620結構CdS 624 and ΖηΟ 622. A photovoltaic cell or a solar cell (e.g., the above device 6A) is constructed as a large area Ρ-η junction. When photons in the sun strike the photovoltaic cell, the photons are reflected through the transparent electrode layer or absorbed. The absorption of the semiconductor layer results in the generation of electron-hole pairs: The photon needs to have more energy than the band_energy to excite the electron ad valorem = into the conduction band. This allows electrons to flow through the material to generate electricity. Complementary positive charges or holes 'flow in the direction of the electron phase with the wire. A too-touch panel with many photovoltaic cells converts the domain to direct current. For thin film solar cell applications, semiconductors based on copper indium dimer ((3)) are particularly attractive due to their high optical (four) and pass (iv) optoelectronic properties. Pastly, these characteristics can be manipulated and adjusted for the specific needs of a given device towel. Wei enough to make the whole layer have better uniformity, and thus reduce the number of re-recording of the film. The tearing increases the quantum efficiency and thus the conversion effect. 201123314 The present invention provides a large for solar panels. A method of fabricating an as and/or CIGS based solar cell on a glass substrate. The device structure diagram depicted in Figure 6 can be used to separate individual domain energy cells on the substrate and connect to each other to form a solar (four) cell plate. Ashamed, the present invention provides a cost effective method of retrofitting thin film solar panels. It should be understood that 'no fineness and indium lanthanescence _ order how (4) achieve the present invention, all benefits. That is, indium may be deposited first, or germanium may be deposited as a thinner plurality of layers of inclusions or stacks. It is to be understood that the present invention is described in the context of the exemplary embodiments and the exemplary embodiments of the present invention, and that there are various modifications or variations that may be made to the skilled person in the art. The spirit and scope of the invention and the scope of the appended patent application. Figure 7 is a self-cleaning __ before the decomposition of the selenide material according to an embodiment of the present invention. This ® is only an example and should not limit the scope of the patent application herein. As shown, the hybrid 7 (10) includes the processing chamber 7〇2 and the end of the chamber *704. The inner surface and the spatial area of the processing chamber 7() 2 are described as an internal processing area 706. In an embodiment, the processing chamber 7〇2 may comprise a quartz tube. The end cap area view shows the inner surface of the end cap 704 of the inner processing region 706. As noted above, the end face 7〇4 and the process chamber 702 are characterized by surface reactivity and/or viscosity for various types of winters substances. For example, under certain conditions, various types of materials may be deposited on the end cap 7〇4 but not on the inner surface of the chamber 7❶2. In a specific embodiment, the end cap region 7〇2 is made of a material having a lower heat than the processing chamber 7〇2 than 19 201123314. In one embodiment, the end cap 704 is comprised of at least a metallic material. Residual selenide 710 may be deposited in internal processing region 706 during the selenization process. According to one embodiment, the temperature gradient can be formed by introducing a mechanical baffle between the inner treatment zone and the end cap region such that convection can carry the residue away from the inner treatment zone and prevent residual selenide 71〇 from depositing inside Processing area 706. It is also to be understood that the embodiments and embodiments described herein are for illustrative purposes only, and that there are various modifications or variations that may be made by those skilled in the art, which are included in the present application. Spirit and scope and the scope of the attached patent application. Figure 8A is a simplified diagram of a self-cleaning furnace at month 1j of decomposition of a selenide material, in accordance with an embodiment of the present invention. This figure is only an example and should not limit the scope of the patent application herein. As shown, the furnace 8A includes a processing chamber 8〇2 and an end cap 804 for the chamber. The inner surface and the spatial region of the processing chamber 802 are traced to the internal processing region 806. In an embodiment, the processing chamber 8〇2 may comprise a quartz tube. The end cap region 8〇8 represents the inner surface of the end cap 8〇4 that is exposed to the inner processing region 806. In one embodiment the 'end cap 804 can be made of a metallic material. During the process of the coded process, residual selenide 810 may have been deposited in the internal processing region 8.6. According to one embodiment, a temperature gradient can be formed by introducing a mechanical baffle between the inner treatment region 806 and the end cap region 8〇8, so that the flow closure closes the residual surface from the inner treatment region. The compound (10) is in the (10) processing region 806. 0 20 201123314 FIG. 8B is a simplified diagram of a self-cleaning furnace during the decomposition of the selenide material and the deposition of 70 selenium at the end cap, in accordance with an embodiment of the present invention. This figure is only an example and should not limit the scope of the patent application herein. As shown, furnace 820 includes a processing chamber 822 and an end cap 824 of the chamber. The inner surface and the spatial region of the processing chamber 822 are depicted as an internal processing region 826. In one embodiment, the processing chamber 822 can include a quartz tube. End cap region 828 represents the inner surface of end cap 824 that is exposed to inner processing region 耵6. In one embodiment, the end cap 824 can be made of a metal material. During the decomposition of the selenide species, the residual material 83, including elemental selenium, is vaporized and carried (by convection by the thermal gradient) from the inner processing zone 826 toward the end cap region 824. Figure 8C is a simplified diagram of a self-cleaning furnace after decomposition of selenide material and deposition of halogen selenium at the end cap, in accordance with an embodiment of the present invention. This figure is only an actual quotation / and should not limit the scope of the patent application in this article. As shown, the furnace 840 includes a process chamber 842 and an end cap 844 for the chamber. The inner surface and the spatial region of the processing chamber 842 are depicted as an internal processing region 846. In one embodiment, the processing chamber 8 can include a quartz officer. End cap region 848 represents the inner surface of end cap 844 that is exposed to inner processing region 846. In one embodiment, the end cap 844 can be made of a metallic material. After the decomposition and deposition of the selenide species, the residual selenide 85 is contained in the end cap region 848. For example, due to the temperature gradient between the end cap and the processing chamber, at least in part, the deposition or condensation of residual telluride 81G is caused. The temperature gradient can be greatly enhanced by increasing the baffle structure used as the permeable barrier. After the formation of the CIS layer is completed and the substrate is removed from the process chamber 842, the residual boot can be mechanically removed with a cloth (e.g., linen, 201123314 = 2 =). It will be appreciated that by subjecting the bismuth and/or its (four) green end to the hull, it is possible to wipe off the residue on the end cap structure. While in various conventional techniques, it is often necessary to clean the interior of the processing chamber from the furnace > Fig. = Fig. 8B and Fig. 8C are diagrams showing the steps of the decomposition of the residual stone cassin and the path at the end cap region where the element is deposited. It should also be understood that the examples and embodiments described herein are for illustrative purposes only, and that various modifications or variations of the present invention may be made to the skilled person M. The spirit and scope of the invention and the scope of the appended patent application. Figure 9 is a self-cleaning coffee after decomposition of the telluride material and deposition of the elemental stone at the end cap, in accordance with an embodiment of the present invention. This level is an example and should not limit the scope of patent application in this document. As shown, the furnace includes an end cap 904 that processes t 902 and the chamber. The inner surface and the spatial region of the processing chamber 9〇2 are described as the inner processing region 906. In one embodiment, the processing chamber 9〇2 may comprise a quartz tube. The end cap region 908 represents the inner surface of the end cap 9〇4 that is exposed to the inner processing region 9〇6. In one embodiment the 'end cap is just made of a metallic material. Residual material 9W is included in end cap region 908 after decomposition and deposition of the bulk material. After the formation of the CIS layer is completed and the substrate is removed from the processing chamber 902, a cloth (e.g., linen, or the like) may be used to mechanically remove residual lithabolite. It should also be understood that the embodiments and implementations described herein are only used for the purpose of the description of the teachings of the present invention. Please select the scope of the application and the scope of the attached patent application. Although specific structures for cis and domain thin film batteries have been primarily described above, other specific as-cut or aGs configurations may be made, for example, without the invention described in the scope of the patent application. Those which are mentioned in the U.S. Patent Nos. 4,611, the entire disclosure of which are incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a transparent substrate having an overlapping electrode layer according to an embodiment of the present invention; FIG. 2 is a composite structure including copper and a film according to an embodiment of the present invention. 2A is a schematic view of a composite structure including a copper indium composite/alloy according to an embodiment of the present invention; FIG. 3 is a schematic view of a furnace according to an embodiment of the present invention; FIG. 5 and FIG. 5A are diagrams showing a temperature distribution of a furnace according to an embodiment of the present invention; FIG. 6A is a schematic view of a temperature distribution of a furnace according to an embodiment of the present invention; FIG. A schematic diagram of a thin film copper indium diselenide device of an embodiment; FIG. 6B is a schematic diagram of a thin film copper indium diselenide device 23 201123314 in accordance with another embodiment of the present invention; FIG. 7 is an embodiment of the present invention. BRIEF DESCRIPTION OF A SELF-Cleaning Furnace Prior to Decomposition of a Selenide Material; FIG. 8A is a simplified diagram of a self-cleaning furnace prior to decomposition of a selenide material in accordance with an embodiment of the present invention; 8B is a schematic diagram of a self-cleaning furnace during decomposition of a selenide material and deposition of elemental selenium at an end cap, in accordance with an embodiment of the present invention; FIG. 8C is a selenide in accordance with an embodiment of the present invention. A simplified diagram of the self-cleaning furnace after decomposition of the substance and deposition of elemental selenium at the end cap; Figure 9 is a self-destruction after decomposition of the selenide material and deposition of the elemental enthalpy at the end cap, in accordance with an embodiment of the present invention A simplified diagram of the cleaning furnace. [Main component symbol description] 100 processing structure, structure 102 metal electrode layer 104 transparent substrate, substrate 200 structure 202 layer 204 layer 206 deposition metal layer, metal layer, layer 208 glass, glass substrate, substrate 210 composite structure, structure, substrate 212 Layer 214 metal electrode layer, layer 216 transparent substrate, glass, substrate 300 furnace 24 201123314 302 processing chamber 304 end cap 306 heating element 308 substrate 310 turbo molecular pump 312 rotary pump 314 gas injection pipe 316 manifold 318 conduction valve 400 method 402 steps 404 Step 406 Step 408 Step 410 Step 412 Step 414 Step 416 Step 418 Step 420 Step 422 Step 424 Step 426 Step 428 Step 600 Support structure 602 Layer 604 Layer 606 Semiconductor layer 608 Metal layer 610 Substrate 201123314 620 Structure
622 ZnO622 ZnO
624 層 CdS 626 半導體層 628層 630玻璃基板 700熔爐 702 處理室 704端帽 706 内部處理區域 708 端帽區域 710 砸化物 800熔爐 802 處理室 804端帽 806 内部處理區域 808 端帽區域 810硒化物 820熔爐 822 處理室 824端帽 826 内部處理區域 828端帽區域 830殘餘物質 840熔爐 842 處理室 844端帽 846 内部處理區域 848 端帽區域 850砸化物 26 201123314 900熔爐 902 處理室 904端帽 906内部處理區域 908端帽區域 910硒化物624 layer CdS 626 semiconductor layer 628 layer 630 glass substrate 700 furnace 702 processing chamber 704 end cap 706 internal processing region 708 end cap region 710 telluride 800 furnace 802 processing chamber 804 end cap 806 internal processing region 808 end cap region 810 selenide 820 Furnace 822 Processing Chamber 824 End Cap 826 Internal Processing Zone 828 End Cap Region 830 Residual Substance 840 Furnace 842 Processing Chamber 844 End Cap 846 Internal Processing Zone 848 End Cap Region 850 Telluride 26 201123314 900 Furnace 902 Processing Chamber 904 End Cap 906 Internal Treatment Zone 908 end cap region 910 selenide