201109450 六、發明說明： 【發明所屬之技術領域】 本揭示内容是有關於在不打破真空的情況下，原位形 成CuInS〗膜層的方法，以及含有所形成之CuInS2膜層的 太陽能元件。 【先前技術】 近年來太陽能相關技術的發展相當快速，其中CuInS2 薄膜因具有高吸收係數而被廣泛用來製造光電元件，例如 薄膜太陽能電池。已知CuInS2薄膜太陽能電池在0.38平方 公分這樣小的面積上，總面積效率可達12.2%(D. Braunger et al., Proc. 25 IEEE Photovoltaic Specialists Conf. IEEE, New York, May 13-17, 1996, p. 1001) » 習知用來形成CuInS2薄膜的方法包括先製備出可做為 前驅物的Cu-In薄膜，接著熱處理該前驅物薄膜，並進行 硫化反應，以形成欲求的CuInS2薄膜。整個製程會需要使 用兩個不同的處理腔室，包括可沉積前驅物薄膜的沉積腔 室，以及用來進行熱處理與硫化反應的反應腔室。製程中， 在完成前驅物薄膜的沉積後，需將所沉積的前驅物薄膜移 出沉積腔室外，轉送到另一反應腔室中，以便進行熱處理 與硫化反應。由於需在不同處理腔室間移送基板，使得製 程變得繁複且傳送過程中容易造成基板被污染。 有鑒於此，此領域需要一種新的解決方案，其能^夠在 不減損CuInS2薄膜本身特性的情況下，藉由簡化製程來減 少基板被污染的機率。 ' 201109450 【發明内容】 因此，本揭示内容第一態樣是提供一種沉積CuInS2薄 : 膜的方法，包含： (a) 提供一基材至一處理腔室中； (b) 以物理性沉積法將錮元素及銅元素分別沉積在該 基材上以形成一具有2層結構之Cu-In薄膜； (c) 熱退火該Cu-In薄膜；及 • (d)硫化該Cu_In薄膜，使形成該CuInS2薄膜； 其中，在所述各步驟之處理期間，始終維持該處理腔 室於真空不破的狀態下。 在一實例中，所述基板是使用任一種選自下列的材料 製成：矽、塑膠、玻璃、第III-V族化合物或氡化物。在一 實施例中，所述步驟(b)中的物理性沉積法為熱蒸鍍且是在 不加熱基板的情況下實施。所述步驟（c)中的熱處理是在約 150°C下進行至少約2小時。所述步驟(d)更包含以下步驟： • 引入含硫氣體到該處理腔室中；加熱該基板至約350°C至 約550°C ;及在約8.5 Pa至約1000 Pa的壓力下處理該基板 約1至2小時。在一特定實例中，所述步驟⑷是在壓力約 為146.7 Pa、溫度約550°C的條件下進行約1小時；在另一 特定實例中，所述步驟(句是在壓力約為1000 Pa、溫度低 於約450°C的條件下進行約1小時。以所述方法形成之 CuInS2薄膜之平均厚度約為1830 nm，且其中銅/銦比約為 1.13。 在另一實例中，更包含重複上述步驟(b)至少3次，使 201109450 形成一具有6層結構的Cu-In薄膜，且所形成之cu_ln薄 膜的整體厚度約為800 nm，且該Cu-In薄膜中各層結構中 的銅/銦比約為1.8。在一特定實例中，所述步驟(d)是在壓 : 力約為146.7 Pa、溫度約550°C的條件下進行約！小時；在 另一特定實例中，所述步驟(d)是在壓力約為1〇〇〇 Pa、溫 度低於約450 C的條件下進行約1小時。以此實例所述方 法形成的CuInS2薄膜之平均厚度約為122〇nm，且其中銅/ 銦比已下降至約1.13。 • 本發明之另一特定實施態樣為提供一種太陽能元件。 此太陽能元件包含一基板，該基板特徵在於包含以前述方 法沉積而成之CuInS2薄膜。在一實例中，該CuInS2薄膜係 以具有2層結構的Cu_In薄膜為起始物，經過熱退火及硫 化處理而形成’其整體厚度約為1830 nm;在另一實例中， 該CuInS2薄獏係以具有6層結構之Cu_In薄膜為起始物， 同樣經過熱退火及硫化處理而形成，且其整體厚度約為 1220 nm。還可進一步在所形成的（^化心薄膜上依序成長 • 硫化锡、本質氧化鋅、掺雜鋁之氧化辞與鎳/銘電極層，以 製成太陽能元件。在一實例中，以上述包含有CuInS2薄膜 之基板來製造太陽能元件，所製成之太陽能元件的光電轉 換效率約為3%。 透過以下的詳細明與附隨之申請專利範圍將可更了解 本揭示内谷的這些及其他特徵。需知以上的概述及以下的 詳細說明僅為例示，用來闡述本揭示内容，而非用以限制 本揭示内容之範_。 201109450 【實施方式】 本發明主要内容在於提供一種原位形成CuInS2膜層 的方法，其特點在於使製程腔室在整個製程處理期間持續 處於真空狀態，亦即，不打破真空的情況下，原位形成 CuInS2膜層，藉此，可在不減損CuInS2膜層特性的情況 下，有效改善先前技藝製程因真空中斷所造成的膜層汙染 問題。 在所揭示的新穎原位製程中，主要是利用熱蒸鍍在基 φ 板上形成適合做為前驅物的Cu-In薄膜，接著，進行熱處 理及硫化反應，即可獲得内含欲求Cuins2膜層的基板。可 將此基板做成應用元件，例如，太陽能元件，供後續應用。 以下將以製造含有CuInS2膜層的基板之實施方式為 例，說明本發明之相關技術内容。 因此，本發明第一態樣是提供一種沉積CUM!膜層的 方法，包含以下步驟： (a) 提供一基材至一處理腔室中； (b) 以物理性沉積法㈣元素及銅元素分別沉積化 基材上以形成一具有2層結構2Cu_In薄膜； (c) 熱退火該Cu-In薄膜；及 ⑷硫化該Cu-In薄膜，使形成該CuinS2薄膜；201109450 VI. Description of the Invention: [Technical Field] The present disclosure relates to a method of forming a CuInS film layer in situ without breaking a vacuum, and a solar element containing the formed CuInS2 film layer. [Prior Art] In recent years, the development of solar-related technologies has been quite rapid, and CuInS2 thin films have been widely used for manufacturing photovoltaic elements such as thin film solar cells because of their high absorption coefficient. CuInS2 thin film solar cells are known to have a total area efficiency of 12.2% over a small area of 0.38 square centimeters (D. Braunger et al., Proc. 25 IEEE Photovoltaic Specialists Conf. IEEE, New York, May 13-17, 1996). , p. 1001) » A conventional method for forming a CuInS2 film includes first preparing a Cu-In film which can be used as a precursor, followed by heat-treating the precursor film, and performing a sulfurization reaction to form a desired CuInS2 film. The entire process will require the use of two different processing chambers, including a deposition chamber where a precursor film can be deposited, and a reaction chamber for heat treatment and sulfurization. In the process, after the deposition of the precursor film is completed, the deposited precursor film is removed from the deposition chamber and transferred to another reaction chamber for heat treatment and vulcanization. Since the substrate needs to be transferred between different processing chambers, the process becomes complicated and the substrate is easily contaminated during the transfer. In view of this, there is a need in the art for a new solution that can reduce the probability of substrate contamination by simplifying the process without detracting from the properties of the CuInS2 film itself. SUMMARY OF THE INVENTION Accordingly, a first aspect of the present disclosure is to provide a method of depositing a CuInS2 thin: film comprising: (a) providing a substrate to a processing chamber; (b) physically depositing Depositing a bismuth element and a copper element on the substrate to form a Cu-In film having a two-layer structure; (c) thermally annealing the Cu-In film; and (d) vulcanizing the Cu_In film to form the film The CuInS2 film; wherein, during the processing of the respective steps, the processing chamber is always maintained in a state where the vacuum is not broken. In one example, the substrate is made of any material selected from the group consisting of ruthenium, plastic, glass, a III-V compound, or a telluride. In one embodiment, the physical deposition in step (b) is thermal evaporation and is carried out without heating the substrate. The heat treatment in the step (c) is carried out at about 150 ° C for at least about 2 hours. The step (d) further comprises the steps of: • introducing a sulfur-containing gas into the processing chamber; heating the substrate to a temperature of from about 350 ° C to about 550 ° C; and treating at a pressure of from about 8.5 Pa to about 1000 Pa The substrate is about 1 to 2 hours. In a specific example, the step (4) is carried out for about 1 hour at a pressure of about 146.7 Pa and a temperature of about 550 ° C; in another specific example, the step is at a pressure of about 1000 Pa. The temperature is lower than about 450 ° C for about 1 hour. The average thickness of the CuInS 2 film formed by the method is about 1830 nm, and wherein the copper / indium ratio is about 1.13. In another example, further included Repeating the above step (b) at least 3 times to form 201109450 into a Cu-In film having a 6-layer structure, and the formed cu_ln film has an overall thickness of about 800 nm, and the copper in each layer structure of the Cu-In film The indium ratio is about 1.8. In a specific example, the step (d) is carried out at a pressure: force of about 146.7 Pa and a temperature of about 550 ° C for about ! hours; in another specific example, The step (d) is carried out for about 1 hour under the conditions of a pressure of about 1 〇〇〇Pa and a temperature of less than about 450 C. The average thickness of the CuInS2 film formed by the method described in the example is about 122 〇 nm, and Wherein the copper/indium ratio has decreased to about 1.13. • Another particular embodiment of the invention provides A solar element comprising a substrate comprising a CuInS2 film deposited by the foregoing method. In one example, the CuInS2 film is based on a Cu_In film having a two-layer structure, and is subjected to heat. Annealing and vulcanization treatment to form 'the overall thickness is about 1830 nm; in another example, the CuInS2 thin tantalum is formed by a Cu_In film having a 6-layer structure, and is also formed by thermal annealing and vulcanization. Its overall thickness is about 1220 nm. It can be further grown on the formed film (sulphide, zinc oxide, zinc oxide, doped aluminum and nickel/Ming electrode layer) to make solar components. In one example, a solar cell is fabricated by using the above-described substrate containing a CuInS2 film, and the solar device produced has a photoelectric conversion efficiency of about 3%. The following detailed description will be better understood. These and other features of the present disclosure are to be understood as illustrative only and are not intended to limit the present disclosure. The present invention provides a method for forming a CuInS2 film layer in situ, which is characterized in that the process chamber is continuously in a vacuum state during the entire process, that is, the vacuum is not broken. In the case of forming a CuInS2 film layer in situ, the problem of film contamination caused by vacuum interruption in the prior art process can be effectively improved without detracting from the characteristics of the CuInS2 film layer. In the middle, a Cu-In film suitable as a precursor is formed on the base φ plate by thermal evaporation, and then a heat treatment and a vulcanization reaction are carried out to obtain a substrate containing a Cuins 2 film layer. The substrate can be made into an application component, such as a solar component, for subsequent applications. Hereinafter, the related art of the present invention will be described by taking an embodiment in which a substrate including a CuInS2 film layer is manufactured as an example. Accordingly, a first aspect of the present invention provides a method of depositing a CUM! film layer comprising the steps of: (a) providing a substrate to a processing chamber; (b) physically depositing (four) elements and copper elements Separating the substrate to form a 2Cu_In film having a 2-layer structure; (c) thermally annealing the Cu-In film; and (4) vulcanizing the Cu-In film to form the CuinS2 film;
其中’在所述各步驟之處理期間，始 室於真空不破的狀態下。 處理J 在本發明方法步驟(a)中，首先提供—⑽至 室中^合用在本發明方法之基板的㈣“ 任-種選自下列的材料:石夕、塑膠、 ： 201109450 物或其之氧化物。至於處理腔室，則可使用任何適合用來 進行物理性沉積的腔室，例如美商應用材料公司生產的 Endura系列之ρνρ腔室。 接著’在本發明方法步驟(b)中，在上述之處理腔室 内’利用物理性沉積方式，依序將銦及銅靶材上的銦及銅 元素’沉積在一基板表面上（此基板是利用靜電、磁力或其 他方式加以固持在一基座上），藉此形成適合做為CuInS^ 薄膜前驅物之具有2層結構的Cu-In薄模。適合的物理性 φ 沉積法包括熱蒸鑛(thermal evaporation)、電子束物理性沉 積（electron beam physical vaporation)、藏鑛沉積（sputter deposition)、脈衝式雷射沉積(pUised iaser deposition)或陰 極電弧放電沉積(cathodic arc deposition)。在一實例中，是 使用熱蒸鑛來沉積此Cu-In薄膜。熱蒸鍍一般是在真空條 件下利用電阻器（electric resistor)加熱鍍膜材料（如，金 屬Cu)使其蒸發並喷鍍在基板或試樣表面，藉此達成沉積 薄膜的目的。所述步驟(b)之特點是在熱蒸鍍期間，藉由轉 φ 動處理腔室中用來固持基板的基座，來使沉積膜層均勻， 但並不加熱該基板。透過在基板上依序沉積銦元素及銅元 素，而形成具有2層結構之Cu_In薄膜，其厚度約為8〇〇 nm。在另一特定實施例中，則是重覆實施步驟(b)至少3 次，進而形成由Cu/In/Cu/In/Cu/In交替堆疊成之具有ό層 結構的Cu-In薄膜。在此Cu_In薄膜中，各層結構中的銅 /銦比例係控制在約I.8左右，且各層具有大致相同的厚 度，使Cu-In薄膜整體厚度約為8〇〇nm。 接著，在步驟(C)中，對所形成之具有2層結構之Cu-In 201109450 薄膜或具有6層結構的Cu-In薄膜實施熱退火處理。一般 來說，此熱退火處理是在約100°C至約200°C的溫度下， 進行約1〜3小時。在一實例中，此熱退火處理是在約150 °(：下進行約2小時。實驗發現，經過熱處理之薄膜，其表 面均勻度較佳。因此，在本發明之較佳實施方式中，是以 經過2小時熱處理的Cu-In薄膜（具2或6層結構）做為起 始物，來進行硫化反應，使Cu-In薄膜完全轉變成CuInS2 薄膜。 在所述步驟(d)中，首先，以適當比例，將適合用來進 行硫化反應的含硫氣體，例如H2S氣體，與惰性載氣混合 成為一種氣體混合物，再將其引入至所述處理腔室中。適 合的載氣包括，但不限於，氦、氮、氖或氩等不會參與硫 化反應的惰性氣體。在一實例中，將由H2S與Ar所共同組 成之一氣體混合物，其中H2S的體積比例約為10%，引入 至該處理腔室中。接著，加熱該含有2或6層結構的Cu-In 薄膜之基板至約350°C至約550°C。然後，在約8.5 Pa至約 1000 Pa的壓力下，使基板與所引入的含硫氣體進行硫化反 應約1至2小時。在一實例中，係以2層結構之Cu-In薄 膜或6層結構之Cu-In薄膜為起始物，在146.7 Pa的壓力 及550°C的硫化溫度下反應，所得CuInS2膜層的平均顆粒 大小分別約為1830 nm及1220 nm。在另一實例中，將腔 室壓力提高到1000 Pa，並以具有2層結構之Cu-In薄膜 為起始物，分別在450°C、500°C及550°C硫化溫度下反應， 所得CuInS2膜層的平均顆粒大小分別約為2000 nm、2100 nm及2230 nm。在另一實施例中，以具有6層結構之Cu-In 201109450 薄膜為起始物，在450°C、500°C及550°C硫化溫度下反應， 所得CuInS2膜層的平均顆粒大小則分別約為1640 nm、 1940 nm 及 2220 nm。 在一特定較佳實例中，所述步驟(d)是在壓力約146.7 Pa、溫度約550°C的條件下進行約1小時。在另一特定較 佳實例中，所述步驟(d)是在壓力約為1000 Pa、溫度低於 約450°C的條件下進行約1小時。在步驟(d)後，所形成之 CuInS2薄膜的平均厚度約為i830nm，且其中鋼/銦比約為 爪至文叼疋’隹從芡騍（a)〜灾騍（α)之所揭示的本發印 方法中，將處理腔室始終保持在不中斷真空的情況下:杀 ，，可避免因腔室真空中斷所造成的膜層汙染問題，並3 提供具有較佳表面形態與粗糙度的CuInS2膜層。 因此，本揭示内容另一態樣是提供一種太陽 此太陽旎元件包含一基板，該基板特徵在於包含一 $方法製造出來之内含CuInS2膜層。在-特定實你丨：以」 _ ^明方法所形成之内含CuInS2膜層之基板來製作，' 二太陽^件在模擬的太陽光下，其光電轉^^ 並非it方式與專有名詞是為了闡述發明内容之用 未特专揭j本揭示内容料。本揭示内容範嘴也、、j， 可輕易】：於此，但習知技藝人士在閱讀過本揭示内J 易推知的其他實施方式。 W内容4 習知定義’=中所使用之所有專業與科學用^ 斤熟悉之意義相同。此外，任何與所*己°° «Λ1 a 201109450 相似或均等之方法及材料皆可應用於本發明方法中。文中 所过·較佳實施方法與材料僅做示範之用。於本申請書中 所提到之所有參考文獻均全體納入參考，以揭露並敘述該 文獻所°己载之相關方法及/或材料。此外，文中所討論之文 獻僅揭露本發明申請曰前之習知技術。並且無任何文獻顯 示本發明内容曾為習知技術所揭露。本發明内容所得到之 實際數據會因個別的實施條件而與本發明揭露於說明書内 容中之數據有所不同。 # ^知若無特别於上下文中清楚記述其他意義，則說明 書，谷及後附，請專利範圍中所使用之如「- (“a” 0Γ an )」與「該(the)」等特定用語均包含其複數形態。 以下將詳細說明本揭示内容較佳實施方式，這些實施 實彳丨已繪示在附隨圖不中。各圖示中相同元件以相 同元件號碼表示。 實施例 • 以下實施例是用來闡明本揭示内容特定態樣並幫助 習知技藝者了解並實施本揭示 内容。但本揭示内容範脅並 不限於這些實施例中。 實施例1製造CuInS2薄膜 1.1製造Cu_In前艇物薄琪 首先，將大小為 2.5 mm X 2.5 mm之玻璃基材放置在 處理腔室中’以靜電卡盤固持住基材。利用抽真空的方 式’使處理腔室的腔壓下降至約2.4 X 10_4 Pa。接著，在 第’’且實驗中’以熱蒸鑛(thermal evaporation)方式將銦元 201109450Wherein the chamber is in a state where the vacuum is not broken during the processing of the respective steps. Treatment J In the step (a) of the method of the present invention, first, (10) to the substrate used in the method of the present invention (4) "any kind of material selected from the group consisting of: Shi Xi, plastic, : 201109450 or Oxide. As for the processing chamber, any chamber suitable for physical deposition can be used, such as the ρνρ chamber of the Endura series manufactured by Applied Materials, Inc. Next, in step (b) of the method of the present invention, Depositing indium and copper elements on the indium and copper targets on the surface of the substrate by physical deposition in the above-mentioned processing chamber (the substrate is electrostatically, magnetically or otherwise held on a substrate) On the seat), a Cu-In thin mold having a two-layer structure suitable as a CuInS^ film precursor is formed. Suitable physical φ deposition methods include thermal evaporation and electron beam physical deposition (electron) Beam physical vaporation), sputter deposition, punished iaser deposition, or cathodic arc deposition. In one example, The Cu-In film is deposited by hot-steaming. The thermal evaporation is generally performed by vacuum coating an electric material (for example, metal Cu) by an electric resistor to evaporate and spray it on the surface of the substrate or the sample. Thereby, the purpose of depositing the film is achieved. The step (b) is characterized in that during the thermal evaporation, the deposited film layer is uniformed by rotating the susceptor in the processing chamber for holding the substrate, but not The substrate is heated, and a Cu_In film having a two-layer structure is formed by sequentially depositing indium elements and copper elements on the substrate, and has a thickness of about 8 〇〇 nm. In another specific embodiment, the steps are repeated. (b) at least 3 times, thereby forming a Cu-In film having a bismuth layer structure alternately stacked by Cu/In/Cu/In/Cu/In. In the Cu_In film, the copper/indium ratio in each layer structure is The control is about 1.8, and each layer has substantially the same thickness, so that the overall thickness of the Cu-In film is about 8 〇〇 nm. Next, in the step (C), the formed Cu-layer having a two-layer structure is formed. In 201109450 film or Cu-In film with 6-layer structure is thermally annealed. Generally speaking The thermal annealing treatment is carried out at a temperature of from about 100 ° C to about 200 ° C for about 1 to 3 hours. In one example, the thermal annealing treatment is carried out at about 150 ° (: about 2 hours). The heat-treated film has a better surface uniformity. Therefore, in a preferred embodiment of the present invention, a Cu-In film (having a 2- or 6-layer structure) which has been heat-treated for 2 hours is used as a starting material. The vulcanization reaction is carried out to completely convert the Cu-In film into a CuInS2 film. In the step (d), first, a sulfur-containing gas suitable for the sulfurization reaction, such as H 2 S gas, is mixed with an inert carrier gas into a gas mixture at an appropriate ratio, and then introduced into the treatment chamber. In the room. Suitable carrier gases include, but are not limited to, inert gases such as helium, nitrogen, helium or argon which do not participate in the sulfurization reaction. In one example, a gas mixture of H2S and Ar will be formed, wherein the volume ratio of H2S is about 10%, which is introduced into the processing chamber. Next, the substrate of the Cu-In film containing the 2 or 6 layer structure is heated to about 350 ° C to about 550 ° C. Then, the substrate is subjected to a vulcanization reaction with the introduced sulfur-containing gas at a pressure of about 8.5 Pa to about 1000 Pa for about 1 to 2 hours. In one example, a 2-layer Cu-In film or a 6-layer Cu-In film is used as a starting material, and the reaction is carried out at a pressure of 146.7 Pa and a vulcanization temperature of 550 ° C to obtain an average of the CuInS 2 film layer. The particle sizes are approximately 1830 nm and 1220 nm, respectively. In another example, the chamber pressure is increased to 1000 Pa, and the Cu-In film having a two-layer structure is used as a starting material, and reacted at 450 ° C, 500 ° C, and 550 ° C vulcanization temperatures, respectively. The average particle size of the CuInS2 film layer is about 2000 nm, 2100 nm, and 2230 nm, respectively. In another embodiment, the Cu-In 201109450 film having a 6-layer structure is used as a starting material, and reacted at 450 ° C, 500 ° C, and 550 ° C vulcanization temperature, and the average particle size of the obtained CuInS 2 film layer is respectively About 1640 nm, 1940 nm, and 2220 nm. In a particularly preferred embodiment, the step (d) is carried out for about 1 hour at a pressure of about 146.7 Pa and a temperature of about 550 °C. In another specific preferred embodiment, the step (d) is carried out for about 1 hour at a pressure of about 1000 Pa and a temperature of less than about 450 °C. After the step (d), the CuInS2 film formed has an average thickness of about i830 nm, and wherein the steel/indium ratio is about the same as that disclosed by the 至(a)~ 骒(α) In the printing method, the processing chamber is always kept without interrupting the vacuum: killing, avoiding the problem of film contamination caused by the interruption of the chamber vacuum, and 3 providing CuInS2 with better surface morphology and roughness. Membrane layer. Accordingly, another aspect of the present disclosure is to provide a solar solar cell element comprising a substrate characterized by comprising a CuInS2 film layer fabricated by a method. In the specific case, you can make it by using the substrate containing the CuInS2 film formed by the method of " _ ^ Ming", and the photoelectric conversion of the two solar parts under simulated sunlight is not the way and proper nouns. It is to clarify the content of the invention. The disclosure of the present disclosure is also readily described herein, but other embodiments of the present disclosure are readily apparent to those skilled in the art. W Content 4 Conventional Definitions All the professions used in the '= are the same as those used in science. In addition, any methods and materials similar or equivalent to those of the present invention can be applied to the method of the present invention. The preferred methods and materials used in the text are for demonstration purposes only. All references cited in this application are hereby incorporated by reference in their entirety in their entirety in their entirety in the extent of the extent Moreover, the text discussed herein merely discloses prior art techniques of the present invention. And there is no literature showing that the present invention has been disclosed in the prior art. The actual data obtained by the present invention differs from the data disclosed in the specification by the present invention depending on the individual implementation conditions. # ^知知 If the other meanings are not specifically stated in the context, the specification, valley and attachments, please use specific terms such as "- ("a" 0Γ an )" and "the" in the patent scope. Both contain their plural forms. The preferred embodiments of the present disclosure are described in detail below, and these implementations have been illustrated in the accompanying drawings. The same elements in the respective drawings are denoted by the same component numbers. EXAMPLES The following examples are intended to clarify specific aspects of the disclosure and to assist those skilled in the art to understand and implement the present disclosure. However, the scope of the present disclosure is not limited to these embodiments. Example 1 Production of CuInS2 Film 1.1 Fabrication of Cu_In Foreboat Thin Qi First, a glass substrate having a size of 2.5 mm X 2.5 mm was placed in a processing chamber to hold the substrate with an electrostatic chuck. The chamber pressure of the processing chamber is lowered to about 2.4 X 10_4 Pa by means of evacuation. Next, in the '' and the experiment', the indium element was heated by thermal evaporation 201109450
素與銅元素分別沉積在基板上，以形成具有雙層結構的 Cu-In前驅物薄膜，厚度約為800 nm。在第二組實驗中， 交替沉積銦元素與銅元素各至少3次，以形成由 Cu/In/Cu/In/Cu/In交替堆疊成之具有6層結構的Cu-In薄 膜。在此Cu-In薄膜中，各Cu-In層中的銅/銦比例係控制 在約1.8左右，且各Cu-In層具有大致相同的厚度，使Cu-In 薄膜整體厚度約為800 nm。在熱蒸鍍期間，藉由轉動該 用來固持基板的靜電卡盤，來使沉薄膜層均勻，但並不加 熱該基板。 接著，在約150°C的溫度下熱處理所沉積的膜層，包 括具有雙層結構的Cu-In前驅物薄膜以及具有6層結構的 Cu-In薄膜’約1或2小時。以低掠角入射X光繞射（glazing incident X-ray diffraction, GIXRD) (Rigaku D/MAX2500) 分析所沉積薄膜的結晶結構，並以掃描式電子顯微鏡 (scanning electron microscopy, SEM)分析薄膜的表面形態。 第1圖為所製成之具有2層或6層結構的cu-ln薄膜 岣以缓 的XRD光譜圖。由圖上可看出，雖然所述製程可成功地 沉積出具有欲求Cuuin9相（第1圖，▲標號所示）之 薄膜，然每一相中仍可發現少量的銅（第i圖，η η 示）。同時，SEM掃描分析還發現，經2小時熱声$號所 膜較僅以1小時熱處理之薄膜，具有更佳的表面^理之薄 示出）。因此，在後續的CuInS2薄膜製程中，=句度（未 過2 物進 小時熱處理的Cu-In薄膜（具2或6層結構) ▲ 行硫化反m。 1.2製造CuInS2薄膜 201109450 以上述實施例1.1所製成之具有2層或6層結構且經 2小時熱處理的Cu-In薄膜做為起始物，以如下步驟進行 硫化處理’以製成欲求的CuInS2薄膜。簡言之，在前述處 理腔室中引入10% H2S/Ar之氣體混合物，並分別在約8.5 Pa、81.3 Pa、146.7 Pa及1000 Pa之不同壓力與介於約350 °C至約550°C的溫度下，進行硫化反應約1至2小時，藉 以產生不同的CuInS2薄膜。 同樣的’以GIXRD來分析所獲得的CuInS2薄膜之結 φ 晶結構，結果示於第2圖中。由第2圖之曲線(A)可看出， 在8.5 Pa壓力及450°C溫度下硫化2小時後，膜層上仍可 觀察到CuuIn9 (曲線a，▲標號所示）與Cu之波峰（曲線 A，△標號所示），表示此溫度與壓力的硫化反應條件，不 足以使Cu-In薄膜被完全硫化。The element and the copper element are respectively deposited on the substrate to form a Cu-In precursor film having a two-layer structure with a thickness of about 800 nm. In the second set of experiments, indium elements and copper elements were alternately deposited at least 3 times to form a Cu-In film having a 6-layer structure alternately stacked by Cu/In/Cu/In/Cu/In. In the Cu-In film, the ratio of copper/indium in each Cu-In layer is controlled to about 1.8, and each Cu-In layer has substantially the same thickness, so that the overall thickness of the Cu-In film is about 800 nm. During the thermal evaporation, the deposited film layer is made uniform by rotating the electrostatic chuck for holding the substrate, but the substrate is not heated. Next, the deposited film layer was heat-treated at a temperature of about 150 ° C, including a Cu-In precursor film having a two-layer structure and a Cu-In film having a six-layer structure for about 1 or 2 hours. The crystal structure of the deposited film was analyzed by glazing incident X-ray diffraction (GIXRD) (Rigaku D/MAX 2500), and the surface of the film was analyzed by scanning electron microscopy (SEM). form. Fig. 1 is a slow XRD spectrum of a cu-ln film having a 2-layer or a 6-layer structure. As can be seen from the figure, although the process can successfully deposit a film having a desired Cuuin 9 phase (Fig. 1, ▲), a small amount of copper can still be found in each phase (i, η η shows). At the same time, the SEM scan analysis also found that the film of the thermoacoustic No. of No. 2 after 2 hours was more thin than that of the film which was heat treated for only 1 hour. Therefore, in the subsequent CuInS2 film process, = degree (Cu-In film (with 2 or 6 layers of structure) which has not been heat treated for 2 hours ▲ is vulcanized and reversed m. 1.2 Manufacture of CuInS2 film 201109450 by the above embodiment 1.1 The resulting Cu-In film having a 2-layer or 6-layer structure and heat-treated for 2 hours is used as a starting material, and is subjected to a vulcanization treatment in the following steps to form a desired CuInS2 film. In short, in the aforementioned processing chamber A gas mixture of 10% H2S/Ar is introduced into the chamber, and the vulcanization reaction is carried out at different pressures of about 8.5 Pa, 81.3 Pa, 146.7 Pa, and 1000 Pa, respectively, at a temperature of from about 350 ° C to about 550 ° C. 1 to 2 hours, to produce different CuInS2 films. The same 'GIXRD' analysis of the obtained CuInS2 film junction φ crystal structure, the results are shown in Figure 2. It can be seen from the curve (A) of Figure 2 After vulcanization at 8.5 Pa pressure and 450 °C for 2 hours, CuuIn9 (curved a, ▲) and Cu peak (curve A, △) are observed on the film, indicating the temperature. The conditions of the vulcanization reaction with the pressure are insufficient to completely cure the Cu-In film. .
實驗發現，對具有2層或6層結構之Cu-In薄膜而言， 當反應室腔壓及反應溫度被分別提高到146.7 Pa與400 °C ’且反應時間維持在1小時左右，可有效改善Cu_In薄 φ 膜被硫化的程度。而且，隨著硫化溫度升高，膜層中Cu-In 的比例也漸漸變少（第2圖，曲線A vs曲線B)，以能量 分散光譜儀（energy dispersion spectroscopy, EDS)分析各成 分元素後可發現，CuInS2薄膜内的Cu/In比例已減少至約 1.13。當反應時間與壓力維持不變而反應溫度提高到5〇〇 它時’更可達到完全硫化的狀態（第2圖，曲線C)，此時 膜層中僅有CuInS2相，且EDS分析顯示，CuInS2薄膜内 的Cu/In比例維持在約M3 ’並未改變。若將反應溫度進 一步提高到1000°C時，則除了 CuInS2相外，還會出現Cu2S 12 201109450 的波峰（第2圖’曲線D);對具有6層結構之Cu-In薄膜 而言’在此l〇〇〇eC的反應溫度下，同樣也會出現Cu2S波 - 峰(結果未示出）。 實驗發現，在146.7 Pa的壓力及550°C的硫化溫度 下’以2層或6層結構之Cu-In薄膜為起始物，所得CuInS2 膜層的平均顆粒大小分別約為1830 nm及1220 nm。若將 壓力提高到1000 Pa ’以具有2層結構之Cu-In薄膜為起 始物，在450°C、500°C及550°C硫化溫度下，所得CuInS2 φ 膜層的平均顆粒大小分別約為2000 nm、2100 nm及2230 nm。類似的’以具有6層結構之Cu-In薄膜為起始物，在 450°C、500°C及550°C硫化溫度下，所得CuInS2膜層的平 均顆粒大小則分別約為1640 nm、1940 nm及2220 nm。 第3圖為依據本發明一特定實施方式，以具有6層結構之 Cu-In薄膜為起始物，在1〇〇〇 Pa的壓力下，分別於(A) 4〇〇 °C ’（B) 450°C ’（C) 500°C 或（D) 550°C 的溫度下硫化 1 小時 後的掃描式電子顯微鏡照片。由電顯照片可估算出在400 °c、450°C、500°C或550°C的硫化溫度下，所獲得CuInS2 膜層的平均顆粒大小分別約為188 nm、380nm、1012 nm 及1709 nm °從以上實驗可觀察到，以具有2層或6層結 構之Cu-In薄膜為起始物，在不同溫度下進行硫化反應， 隨著硫化溫度上升，膜層厚度也會跟著升高，同時，硫化 反應時的壓力愈高，顆粒成長愈快速，粒徑愈小，膜層表 面粗糙度也愈高，如第4圖所示。 接著，以配備有電腦控制器KEITHLEY 2400電源計之 4點碳針來測量所製成之（^11182膜層的表面電阻。實驗發 13 201109450 現，依據本發明方法製成之CuInS2膜層的表面電阻相當 低’約在ΙΟ^Ω-cm左右。舉例來說，在146.7 pa壓力及 550°C硫化溫度下’以具有2層或6層結構之Cu-Ιη薄膜為 起始物所製成的CuInS2膜層的表面電阻，分別為〇 81Ω -cm及0.46 Ω-cm;若將反應壓力提高到1000 Pa，則所製 成的CuInSs膜層的表面電阻分別為0.5〇Q-cin及0.51Ω -cm。此結果與先前技藝中所報導之以熱蒸鍍接續以h2S 硫化製程（參見 Antony et al” Sol. Emergy Mater. Sol. Cells 81 (20〇4) 4〇2)、電子束蒸鍍製程（參見 park et al.，Sol. Emergy Mater. Sol. Cells 49 (1997) 365)或喷霧熱解製程 (參見€杜>^&〇61&1.，€.11.0^111 11(2008) 1016)所製造而成 的CuInS2膜層的表面電阻一致。 接著，以光學顯微鏡(PerkinElmer Lambda 950)來測量 依據所述步驟製成之CuInS2膜層的各種光學性質，結果示 於第5及6圖。第5圖為以具有2層或6層結構之Cu-In 薄膜為起始物在包括450°C、500°C或550°C之溫度下硫化 1小時後所產生的CuInS2膜層在各波長下的吸收係數 圖。結果顯示’某些CuInS2膜層具有超過ΙΟ'ηΓ1的吸收 係數，且此吸收係數與膜層的表面粗糙度有關’膜層的表 面粗糙度愈高，其吸收係數也愈高’如第6圖所示。 其他實施例 上述實施例1所製成之CuInS2膜層可應用在太陽能電 池元件上。 依照一般製造薄族太陽能電池的方法’依序在玻璃基 201109450 板上沉積一層約400 nm的金屬背電極（例如，鉬金屬）、 一層約1〜2 μιη的吸收層（例如，依據實施例1所製成之 CuInS2膜層）、一層約50nm的緩衝層（例如，CdS)、一層 約100 nm的本質氧化鋅、一層約500 nm的氧化鋅以及 一層頂端電極層（例如，鎳/銘電極），進而製造出一太陽能 元件。此太陽能元件在太陽模擬光源下的光電轉換率約為 3%。 φ 產業利用性 本揭示内容提供利用在不打破真空的方式下，原位形 成CuInS2膜層的方法，相較於先前技藝，本發明方法可在 不減損CuInS2膜層特性的情況下，有效改善先前技藝製程 中膜層易遭受汙染的問題。以本發明方法製成之包含有 CuInS2膜層之基板可用來製造太陽能元件。 雖然本揭示内容已以實施方式揭露如上，然其並非用 φ 以限定本揭示内容，任何熟習此技藝者，在不脫離本揭示 内容之精神和範圍内，當可作各種之更動與潤飾，因此本 揭示内容之保護範圍當視後附之申請專利範圍所界定者為 準。 【圖式簡單說明】 為讓本揭示内容之上述和其他目的、特徵、優點與實 施例能更明顯易懂，所附圖式之說明如下： 第1圖為依據本發明一實施方式，以150°c熱處理過 15 201109450 之具有雙層結構的Cu-In前驅物薄膜的XRD光譜圖； 第2圖為依據本發明一實施方式分別以具有2或6層 結構之Cu-In薄膜為起始物所製成之CuInS2薄膜的XRD 光譜圖，其中（A)為具有6層結構之Cu-In薄膜在8.5 Pa、 450°C下硫化2小時，（B)為具有2層結構之Cu-In薄膜在 146.7 Pa、550°C下硫化1小時，（C)為具有6層結構之Cu-In 薄膜在146.7 Pa、550°C下硫化1小時，以及（D)為具有2 層結構之Cu-In薄膜在1000 Pa、500°C下硫化1小時後之 XRD光譜圖； 第3圖為依據本發明一實施方式，以具有6層結構之 Cu-In薄膜為起始物，在1000 Pa下於（A) 400°C，（B) 450 °C，（C) 500°C或（D) 550°C的溫度下硫化1小時後的CuInS2 薄膜的掃描式電子顯微鏡照片； 第4圖為依據本發明一實施方式，以2層或6層結構 之Cu-In薄膜進行硫化反應，所得CuInS2膜層之顆粒大小 與硫化溫度或表面粗糙度間的關係； 第5圖為以具有2層或6層結構之Cu-In薄膜為起始 物在包括450°C、500°C或550°C之溫度下硫化1小時後所 產生的CuInS2膜層在各波長下的吸收係數圖；及 第6圖為依據本發明一實施方式所製成之CuInS2膜層 的吸收係數與表面粗糙度的關係圖。 【主要元件符號說明】 無It was found that for Cu-In films with two or six layers, the chamber pressure and reaction temperature were increased to 146.7 Pa and 400 °C respectively, and the reaction time was maintained at about 1 hour, which was effective. The extent to which Cu_In thin φ film is vulcanized. Moreover, as the vulcanization temperature increases, the proportion of Cu-In in the film layer gradually decreases (Fig. 2, curve A vs curve B), and the components of each component can be analyzed by energy dispersion spectroscopy (EDS). It was found that the Cu/In ratio in the CuInS2 film has been reduced to about 1.13. When the reaction time and pressure are maintained and the reaction temperature is increased to 5 〇〇, it is more fully sulphided (Fig. 2, curve C), at which time there is only CuInS2 phase in the film, and EDS analysis shows that The Cu/In ratio in the CuInS2 film was maintained at about M3' unchanged. If the reaction temperature is further increased to 1000 ° C, in addition to the CuInS2 phase, the peak of Cu2S 12 201109450 (Fig. 2 'curve D); for the Cu-In film with 6-layer structure, 'here At the reaction temperature of l〇〇〇eC, a Cu2S wave-peak also appears (results not shown). It was found that the average particle size of the CuInS2 film was about 1830 nm and 1220 nm, respectively, starting from a Cu-In film of two or six layers at a pressure of 146.7 Pa and a vulcanization temperature of 550 °C. . If the pressure is increased to 1000 Pa' and the Cu-In film having a two-layer structure is used as the starting material, the average particle size of the obtained CuInS2 φ film layer is about 450 ° C, 500 ° C and 550 ° C vulcanization temperature, respectively. It is 2000 nm, 2100 nm and 2230 nm. Similarly, using a Cu-In film with a 6-layer structure as the starting material, the average particle size of the obtained CuInS2 film layer at 450 ° C, 500 ° C and 550 ° C vulcanization temperature is about 1640 nm, 1940, respectively. Nm and 2220 nm. Figure 3 is a diagram showing a Cu-In film having a six-layer structure starting from (A) 4 〇〇 ° C '(B) under a pressure of 1 〇〇〇 Pa according to a specific embodiment of the present invention. Scanning electron micrographs after vulcanization at 450 ° C '(C) 500 ° C or (D) 550 ° C for 1 hour. It can be estimated from the electric photograph that the average particle size of the CuInS2 film obtained at 400 °C, 450 °C, 500 °C or 550 °C is about 188 nm, 380 nm, 1012 nm and 1709 nm, respectively. ° It can be observed from the above experiment that the Cu-In film with two or six layers is used as the starting material, and the vulcanization reaction is carried out at different temperatures. As the vulcanization temperature increases, the film thickness also increases. The higher the pressure during the vulcanization reaction, the faster the particles grow, the smaller the particle size, and the higher the surface roughness of the film layer, as shown in Fig. 4. Next, the surface resistance of the film was measured by a 4-point carbon needle equipped with a computer controller KEITHLEY 2400 power meter. Experiment 13 201109450 The surface of the CuInS2 film layer produced by the method of the present invention is now The resistance is quite low 'about ΙΟ^Ω-cm. For example, at a pressure of 146.7 pa and a vulcanization temperature of 550 ° C, it is made of a Cu-Ιn film having a 2-layer or a 6-layer structure. The surface resistance of CuInS2 film layer is 〇81Ω -cm and 0.46 Ω-cm respectively; if the reaction pressure is increased to 1000 Pa, the surface resistance of the formed CuInSs film layer is 0.5〇Q-cin and 0.51Ω, respectively. Cm. This result is reported in the prior art by thermal evaporation followed by the h2S vulcanization process (see Antony et al" Sol. Emergy Mater. Sol. Cells 81 (20〇4) 4〇2), electron beam evaporation process (See Park et al., Sol. Emergy Mater. Sol. Cells 49 (1997) 365) or spray pyrolysis process (see €Du >^&〇61&1., €.11.0^111 11 (2008) 1016) The surface resistance of the CuInS2 film layer produced is the same. Next, it is measured by an optical microscope (PerkinElmer Lambda 950). The various optical properties of the CuInS2 film layer produced according to the above steps are shown in Figures 5 and 6. Figure 5 shows the Cu-In film having a 2- or 6-layer structure starting from 450°. Absorption coefficient diagram of CuInS2 film layer produced at C, 500 ° C or 550 ° C for 1 hour after vulcanization at various wavelengths. The results show that 'some CuInS2 film layer has an absorption coefficient exceeding ΙΟ 'ηΓ1, and this The absorption coefficient is related to the surface roughness of the film layer. The higher the surface roughness of the film layer, the higher the absorption coefficient is as shown in Fig. 6. Other Embodiments The CuInS2 film layer prepared in the above Example 1 can be applied. On the solar cell element. According to the general method for manufacturing a thin-wall solar cell, a metal back electrode (for example, molybdenum metal) of about 400 nm and a layer of about 1 to 2 μm are deposited on the glass substrate 201109450. For example, a CuInS2 film layer prepared according to Example 1, a buffer layer of about 50 nm (for example, CdS), a layer of about 100 nm of essential zinc oxide, a layer of about 500 nm of zinc oxide, and a layer of top electrode layers (for example) , nickel / Ming electrode), A solar component is manufactured. The photoelectric conversion rate of the solar component under a solar analog light source is about 3%. φ Industrial Applicability The present disclosure provides a method for forming a CuInS2 film layer in situ without breaking a vacuum. Compared with the prior art, the method of the present invention can effectively improve the problem that the film layer is susceptible to contamination in the prior art process without detracting from the characteristics of the CuInS2 film layer. The substrate comprising the CuInS2 film layer produced by the method of the present invention can be used to fabricate solar elements. Although the disclosure has been disclosed in the above embodiments, it is not intended to limit the disclosure, and any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the disclosure. The scope of the disclosure is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present disclosure will become more apparent and understood. The XRD spectrum of the Cu-In precursor film having a two-layer structure after heat treatment of 15 201109450; FIG. 2 is a schematic diagram of a Cu-In film having a structure of 2 or 6 layers, respectively, according to an embodiment of the present invention. XRD spectrum of the prepared CuInS2 film, wherein (A) is a Cu-In film having a 6-layer structure and vulcanized at 8.5 Pa, 450 ° C for 2 hours, and (B) is a Cu-In film having a 2-layer structure. Vulcanized at 146.7 Pa, 550 ° C for 1 hour, (C) is a Cu-In film having a 6-layer structure at 146.7 Pa, 550 ° C for 1 hour, and (D) is a Cu-In having a 2-layer structure. The XRD spectrum of the film after vulcanization at 1000 Pa and 500 ° C for 1 hour; FIG. 3 is a schematic diagram of a Cu-In film having a 6-layer structure starting at 1000 Pa according to an embodiment of the present invention. A) Scanning electricity of CuInS2 film after vulcanization for 1 hour at 400 °C, (B) 450 °C, (C) 500 °C or (D) 550 °C Fig. 4 is a view showing the relationship between the particle size of the obtained CuInS2 film layer and the vulcanization temperature or surface roughness by vulcanization reaction of a Cu-In film of two or six layers according to an embodiment of the present invention; The figure shows a CuInS2 film layer produced by vulcanization at a temperature of 450 ° C, 500 ° C or 550 ° C for 1 hour using a Cu-In film having a 2-layer or 6-layer structure at each wavelength. The absorption coefficient map; and Fig. 6 is a graph showing the relationship between the absorption coefficient and the surface roughness of the CuInS2 film layer produced according to an embodiment of the present invention. [Main component symbol description] None