TW201038769A - Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery - Google Patents

Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery Download PDF

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Publication number
TW201038769A
TW201038769A TW99103930A TW99103930A TW201038769A TW 201038769 A TW201038769 A TW 201038769A TW 99103930 A TW99103930 A TW 99103930A TW 99103930 A TW99103930 A TW 99103930A TW 201038769 A TW201038769 A TW 201038769A
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Taiwan
Prior art keywords
substrate
furnace
furnace chamber
gas
oxygen
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TW99103930A
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Chinese (zh)
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Immo Koetschau
Dieter Schmid
Robert Michael Hartung
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Centrotherm Photovoltaics Ag
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The present invention concerns a process for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers with a recovery of chalcogen, as well as a device for carrying out the process. The aim of the invention is to provide a rapid and readily executable process for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers, as well as a device suitable for carrying out the process with as small as possible primary consumption of chalcogens. This is achieved by heating substrates in a furnace at approximately atmospheric pressure to a final temperature in the range 400 DEG C to 6000 DEG C and transforming them into semiconducting layers in an atmosphere formed from a mixture of at least one carrier gas and chalcogen vapour, wherein chalcogen vapour not consumed in the reaction is made available to the process again via exhaust gas recirculation.

Description

201038769 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種利用氧族元素回收將平坦基板上的 金屬先驅物薄膜熱轉變成半導體薄膜之方法及裝置。 【先前技術】 將太陽能轉變為電能是一種經濟及環保的發電方式， 纟需製造一尚效率的太陽能電池，製造應使用最少的材料 及此量此處係指薄膜太陽能電池，尤其是以半導體化合 物，如銅銦鎵硒（CIGS)為基礎之太陽能電池。 本發明製造半導體薄膜之方法為一種多段式製程。金 屬先驅物可含銅、鎵、銦。其可以習知技術，例如賤鍵’ 而被塗佈在基板上，且該基板可是一含鉬薄膜之玻璃基 板。而在第二步驟之溫度處理中，金屬先驅物在一含氧族 疋素的氣體環境，特別是硒及/或硫的氣體環境令被轉變成 半導體薄膜，尤其是CIGS薄膜。氧族元素在室溫（亦即約 〇 2(rc) 態，且在約35(TC以上的溫度時被蒸發。 此種具半導體薄膜之基板可進一步被加工成太陽能模 組。對於良好效率為重要的是，需儘量將金屬先驅物完全 轉變成基板表面上具相同薄膜厚度及均勻組成成分的半 體薄膜。 熱轉變該先驅物薄膜成為半導體薄膜之方法為習知’ 且已知其在真空中進行。真空製程的問題在於轉變時間（亦 即製程時間）極長。如此而不利於工業製造，因冗長的製 程時間代表著低生產率。而解決方法為，同時使用多部機 201038769 然而這些方 器，但如此則須提高投資成本’或加速製程 法在習知技術中不可能實施。 〜，習知尚有一種熱轉變該先驅物薄膜成為半導體 ==其係在氣體環境條件下及輸入含氣之氣體(例 如風化硒，進行熱轉變（見EP 0 318 3i5 A2)。作因使用 有毒氣體（例如氫化硒），仍為有問題之熱轉變方法。 咖m提出一種在一基板上製造黃鋼礦半導 之方法，其將含金厲（例如銅、銦、鎵）之基板在一惰 性製程氣體中以至少觀秒之加熱速度，加熱至至少3贼 之終溫度4維持在終溫度卿而使基板 被暴露於相對於銅、銦、鎵為過剩之硫或财。如此而在 基板的薄膜結構上方小於5mm之距離產生封裝。硫或砸之 分壓高於原成分銅、銦、鎵。但其未提出一種分成多個不 同溫度部份，適用連續通過法之爐。 國際專利申請案PCT/EP 2〇〇8/〇〇7466提出一種將任意 基板上之金屬薄膜簡單及快速熱轉變成半導體薄骐之方法 及進行該方法之裝置。 其方法為將至少塗佈一層金屬先驅物薄膜之基板在一 具不同溫度部份的爐中之大氣壓力環境下，以多個步驟而 由—預設溫度加熱至400°C至60(TC之終溫度，並保持在該 終溫度下在一載氣與氧族元素蒸氣之混合物中被轉變成半 導體薄膜。 如此可在明顯低於10K/秒之加熱速度下得到良好的半 導體薄膜。 201038769 而先鈾技術必須確俾，、去， „ ± 保達到終溫度時，存在足夠的氧 鈿元素’以便使金屬先驄一 元*私物缚膜完全轉變成半導體薄膜。 但此處需有過剩之羞 、 氣知兀素。未被反應之過剩氧族元 素破與載軋一起由—麻名、s ^ 歷乳通道而排出爐外。依據先前技 術，可由排出的氧族开去甘 > ]孜 、素瘵軋/载氣混合物’亦即廢氣，谏 出氧族元素’而作為廢物被清除。 〜 【發明内容】201038769 VI. Description of the Invention: [Technical Field] The present invention relates to a method and apparatus for thermally converting a metal precursor film on a flat substrate into a semiconductor film by recovery of an oxygen group element. [Prior Art] Converting solar energy into electrical energy is an economical and environmentally friendly way of generating electricity. There is an urgent need to manufacture an efficient solar cell. The minimum amount of materials should be used in manufacturing. This amount refers to thin film solar cells, especially semiconductor compounds. Such as copper indium gallium selenide (CIGS) based solar cells. The method of manufacturing a semiconductor thin film of the present invention is a multi-stage process. Metal precursors may contain copper, gallium, and indium. It can be coated on a substrate by a conventional technique such as a ruthenium bond, and the substrate can be a glass substrate containing a molybdenum film. In the temperature treatment of the second step, the metal precursor is converted into a semiconductor film, especially a CIGS film, in a gaseous environment of an oxygen-containing halogen, particularly selenium and/or sulfur. The oxygen element is at room temperature (ie, about (2 (rc) state, and is evaporated at a temperature of about 35 (temperature above TC.) The substrate with the semiconductor film can be further processed into a solar module. For good efficiency It is important to completely convert the metal precursor into a half-film with the same film thickness and uniform composition on the surface of the substrate. The method of thermally converting the precursor film into a semiconductor film is known and is known in vacuum. The problem with the vacuum process is that the transition time (ie, the process time) is extremely long. This is not conducive to industrial manufacturing, because the lengthy process time represents low productivity. The solution is to use multiple machines at the same time 201038769. However, it is necessary to increase the investment cost' or the accelerated process method is impossible to implement in the conventional technology. ~, there is still a thermal transformation of the precursor film into a semiconductor == its system under gas environment conditions and input Gas of gas (such as weathering selenium, for thermal conversion (see EP 0 318 3i5 A2). The use of toxic gases (such as selenium hydride) is still problematic. Thermal conversion method. A method for manufacturing a semi-steel of a smectite on a substrate, which comprises a substrate containing gold (for example, copper, indium, gallium) in an inert process gas at a heating rate of at least a second. Heating to at least 3 thieves, the final temperature 4 is maintained at the final temperature to expose the substrate to excess sulfur or copper relative to copper, indium, or gallium. Thus, a package is produced at a distance of less than 5 mm above the film structure of the substrate. Or the partial pressure of bismuth is higher than the original components of copper, indium and gallium. However, it does not propose a furnace which is divided into a plurality of different temperature parts and is suitable for continuous passing. International Patent Application PCT/EP 2〇〇8/〇〇7466 A method for simply and rapidly converting a metal thin film on a substrate into a semiconductor thin film and a device for carrying out the method are provided. The method is to apply a substrate of at least one metal precursor film to a furnace at different temperature portions. In an atmospheric pressure environment, heated in a plurality of steps from a preset temperature to 400 ° C to 60 (the final temperature of TC, and maintained at the final temperature in a mixture of carrier gas and oxygen elemental vapor change Semiconductor film. This results in a good semiconductor film at a heating rate significantly lower than 10 K / sec. 201038769 And the uranium technology must be confirmed, go, „ ± when the final temperature is reached, there is enough oxygen ' element in order to The metal first *1 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私The milk passage is discharged out of the furnace. According to the prior art, the discharged oxygen group can be removed as a waste by the sputum, the sputum rolling/carrier gas mixture, that is, the exhaust gas, and the oxygen element is extracted. SUMMARY OF INVENTION

Ο 本毛明之目的在於提供一種將金屬先驅物薄膜以 品質熱轉變成半導體薄膜之方法及裝置。其中廢棄氧族元 素被明顯減少。較低之廢棄量簡化了生產方法並降低了成 本’因投入較少的氧族元素。 *依據本發明之方法，其係將至少塗佈一層金屬先驅物 薄膜之基板在一爐中之大氣壓力環境下，加熱至峨至 600。。之終溫度，並在一載氣與氧族元素蒸氣之混合物中被 轉變成半導體薄膜，—部份未被使用於反應之氧族元素蒸 氣並被回收到製程令。 ’ 本發明中氧族元素較佳為砸。本發明中載氣較佳為一 惰性氣體，更佳為氮。 本發明一較佳設計中’基板在一分成一或多個溫度部 份的爐中被以多個步驟加熱至一預設溫度。 本發明爐争之基板較佳被同時逐步由—部份輸送至下 一部伤’且在每一部份中的停留時間相同。 本發明中基板停留時間可為20至200秒，較佳為4〇至8〇 秒’更佳是50至70秒，最佳為60秒。 201038769 本：明中基板之加熱分段式可由室溫加熱至例如 太:戰’終溫度為㈣，其不需被超過。 發明基板可接著以至少—步驟被冷卻至室溫。 本發明準備需要的氧族元素蒸氣以使金屬先驅物薄膜 二導體薄膜時’可使基板在進入爐内之前先至少被 塗佈一層軋族元素薄膜。 本發明基板上的氧族元素薄膜較每味，备& _ * 爐内被完全蒸發’而在爐中進行轉變製裎。、u在 :發：中氧族元素薄膜較厚時，氧族元素可只部份蒸 ，、可-部份以炫化之氧族元素轉變金屬先驅物薄膜。 塗佈族元素薄膜較佳可利用氧族元素蒸鑛而被 ==屬先驅物薄膜上。其可在大氣條件下以連續通過 =明中由基板快速蒸發氧族元素會使氧族元素沿著 爐m皮動。如此會導致局部在到達終溫度時的氧族 不足’而使得局部之金屬先驅物未完全轉變為半 本發明之廢氣回收除了減少投入之氧族元素外，並對 於爐室中氧族元素濃度有正面的作用。 當氧族元素薄膜較薄時，由—材料源輸入氧族… 1可確'平整性及有足夠的氧族元素漠度，其並可應用 於基板上無氧族元素薄膜時。 201038769 *，基板事先塗佈有—層氧族元素薄膜時，可由一外部 的蒸乱源另仃將氧族元素蒸氣輸入爐室中，或在爐室内部 設一内部的蒸氣源。 本發月之另—特徵為，金屬先驅物以接續濺鍍銅/鎵及 钢而產生。 為達此目的，可使例如玻璃製成的基板首先㈣鍵一 * :厂後在其上方由銅/鎵靶材真空濺鍍第二層銅/鎵薄 〇 冑’最後則以銦姉真空缝第三層銦薄膜。鉬的塗佈在 第濺鍍'備中進行，銅/鎵及銦車則在一第二濺鍍設備 中進行。 然後加熱基板’較佳在無氧與氫，或只存在最少量的 氧與氫分壓下，而轉變金屬先驅物。 本發明目#尚可由本發明之裝i而達成，本發明之裝 置其包括-爐，其爐室具有一基板入口一基板出口在 土板入口的氣體閘門，及一在基板出口的氣體閘門；-基 朽送/、，及將氧族元素蒸氣/載氣混合物排出之廢氣 通道’廢氣通道處設有—流量分配器及/或—回收裝置，其 使未使用於反應之氧族元素可被回收至爐室。此處較佳可 在流量分配器與爐室《間設一回收通道。 本發明中氧族元素較佳為硒。 成本發明中氣體閘門可利用適當的氣流使開σ兩側的氣 體環丨兄彼此分離，而無須在開口設門。 本發明之一較佳設計中，氣體閘門兩側的氣流可被獨 立分開調整。 201038769 ’亦可 更佳為 本發明中爐室氣體閘門可至少由兩個氣簾構成 在氣簾之間增設一抽氣裝置。 本發明中保護氣體/載氣較佳為一惰性氣體， 氮。 本發明中基板入口、基板出口及氣體間門使得裝置可 以在大氣壓力及定義的剩餘氣體條件下，進行連續通過 法。較佳為無氧條件下，進行連續通過法。 一本發明中輸送工具及入口與出口可使得基板可進入爐 至中，通過爐室，然後在金屬先驅物轉變為半導體薄膜之 f發明、—較佳實施例中’氧族元素蒸氣/載氣混合物經 廢，通道被輸送至一流量分配器，而被分成兩股可調整 氣刀"II·第廢氣分流被回收至爐室中，較佳是被 收至爐室開端部。 本發明之第二廢氣分流 通道排出。 即剩餘廢氣，被一剩餘廢氣 _本發明之剩餘廢氣可被過濾，然後排出。廢棄之氧族 元素需被清除或再利用。 、本發明另—較佳實_中，《量分配器可與-回收裝 2連接n回收裝置之組件。回收裝置將第二廢氣分 、（剩餘廢棄）申所含的氧族元素抽出，而併入第一廢氣 :流中’故回收回爐室的氣體提高了氧族元素的量。被排 A剩餘廢氣因此含有較低的氧族元素漠度，故廢棄之氣 U素較少。„提高了製財的氧族元素含量。 201038769 本發明裝置一較佳實施例中，爐室、流量分配器、回 收裝置、廢氣通道及回收通道内部的一或多個壁的溫度被 設定及保持在高於氧族元素之凝結溫度。 如此而防止氧族元素凝結於其内壁並附著在其上。其 會導致氧族元素損失及麻煩的維修。 本發明裝置壁溫不需皆相同，尤其是爐室中。本發明 爐室可分成多段以…如接續的不同溫度部份。 ' 0 本發明爐室、流量分配器、回收裝置、廢氣通道及回 收通道内壁及不同溫度部份的溫度可藉助一加熱及冷卻系 統而獨立分開調整。 本發明一較佳設計中，各段彼此隔熱。如此可使相鄰 的部份被加熱至不同的溫度。 本發明爐至可整體及/或各段分別隔熱，亦降低加熱之 消耗能量。 本發明一較佳實施例中，爐室之壁由石墨構成。 本發明分成多段之爐室中的輸送工具較佳可逐步及同 © 時將所有在爐室中的基板輸送至下一段中。 本發明由於基板被逐步及同時輸送至下一段，故基板 在每段中的停留時間相同，可例如為60秒。 本發明為改良爐室中之無氧及氫，爐室可被一殼體包 覆’其較佳具一基板入口及一基板出口。 本發明殼體較佳由高級鋼構成。 本發明殼體較佳具一分開的殼體抽氣裝置，其可被一 保護氣體沖刷。 201038769 在本發明一較佳實施例中’殼體具一分開的冷卻系 統。如此熱可被排出爐室。 此外，本發明殼體中較佳尚設有一偵測氣體及/或氣體 /農度之感測器，更佳為一氧感測器及/或一 ^^2§6感測器。 本發明氧感測器可偵測到進入殼體與爐室之間的氧。 本發明H2Se感測器作用在於確保安全，其可在出現氫 化硒時即時發現而提出警告。 以下將依據附圖詳細說明本發明之一實施例。 【實施方式】 圖1顯示一爐室丨，其具一廢氣通道7。廢氣通道7設有 一流量分配器2及一回收裝置3。流量分配器2及回收裝置3 整合成一單元。一回收通道8由流量分配器2延伸至爐^1 , 而連接爐室1之開端。回收裝置3連接一剩餘廢氣通道9,其 排出剩餘廢氣。爐室i設有―人口側及出口側氣體問門4。 爐室i内部設有-輸送裝置1Q’其具複數個前後排列之 輸送滾筒。輪送裝置_用於使基板u通過爐“。爐室】 前後分成多個部分，其被獨立控溫且互為熱隔離。為清楚 說明’各個部分不被分開顯示，圖中爐室i相較於真正的裝 置長度縮短，壁之中間部分被以虛線顯示。 、 氮 在本實施例中本裝置所進行製程之保護氣體/載氣為 圖·示氣體閘門4。多段式氣簾各包含㈣並排 軋氣簾流入口 5，其各產生一從上方 " .ΒΒ 乃叹伙下方向對向流動之 虱〜。閘門中間部分產生一低過壓， 、匕以及一抽氣裝置，其 201038769 由上方及下方位在兩氮氣氣廉氣流入口之間的流出口 6構 成。該裝置使氣簾兩側的氣流可被分開獨立調整。 氣簾使基板可在大氣壓力下及定義的剩餘氣體條件 下’尤其是無氧’以連續通過法通過爐。 在本實施例中爐室1之壁由石墨製成，且被一未示出的 高級鋼殼體包覆，其具一分開的抽氣裝置及被氮氣沖刷。 在本實施例中藉助加熱及/或冷卻系統可沿爐室中設 0 定不同之溫度。 在本實施例中被塗佈銅/鎵、銦及砸層之基板u可被輸 送裝置10由入口側氣體閘門4進入爐室丨。基板“由該處逐 步通過爐室1各部分，最後由爐室i末端之出口側氣體閘門4 離開。 在本實施例中本裝置所進行製程爐室每一部份之停留 時間為60秒。 ^爐室1開端處，基板11上的硒開始熔化，其為一較薄之 __可被全蒸發。碼蒸氣與氮混合而構成—砸蒸氣/载 氣混合物。該混合物可利用爐内部之氣流控制，穿過爐室丨 離開設備中的基板11而被輸送至廢氣通道7。氣流無相反方 向之輸送。 氧族元素薄膜較厚時’氧族元素亦可只被部分蒸發。 、可。Ρ伤以熔化之氧族元素轉變金屬先驅物薄膜。 氣體閘門4兩側及廢氣通道7中的氣流可被獨立分開調 土。爐室1中氣流由入口 5± ^ ^ ^ 主廢乳通道7之速度需配合基板11 201038769 之輸送速度，以使達到反應溫度時，有多餘之叾西可轉變金 屬先驅物薄膜成為CIGS薄膜。 未被使用之站經廢氣通道7而被排出。廢氣通道7將石西 蒸氣/載氣混合物輸送至流量分配器2。 流量分配器2將廢氣分成兩股可調整之廢氣分流。 第一廢氣分流經回收通道8而被回收，並流入爐室1開 端處。回收裝置3同時將第二廢氣分流中所含的一部份氧族 元素氧化物抽出’而併入第一廢氣分流中。 第二廢氣分流之剩餘部分，即剩餘廢氣，只含有少量 的氧族元素氧化物。該剩餘廢氣經剩餘廢氣通道9過濾排 出廢棄之乳族元素需被清除或回收再利用。 該回收減少硒之損失，故可降低硒之用量。 【圖式簡單說明】 圖1係本發明裝置之縱載面圖。 圖2係本發明裝置之部分圖，即實施例中使用之氣體間門 【主要元件符號說明】 1爐室 2 流量分配器 3 回收裝置 4氣體閘門 5 流入σ 6 流出口 12 201038769 7 廢氣通道 8 回收通道 9 剩餘廢氣通道 10輸送裝置 11基板The purpose of the present invention is to provide a method and apparatus for thermally converting a metal precursor film into a semiconductor film by quality. Among them, the waste oxygen species are significantly reduced. The lower waste simplifies the production process and reduces the cost of 'oxygen elements' due to less investment. * According to the method of the present invention, a substrate coated with at least one layer of a metal precursor film is heated to a crucible to 600 under atmospheric pressure in a furnace. . The final temperature is converted into a semiconductor film in a mixture of carrier gas and oxygen elemental vapor, part of which is not used in the reaction of the oxygen element vapor and is recycled to the process. The oxygen element in the present invention is preferably ruthenium. The carrier gas in the present invention is preferably an inert gas, more preferably nitrogen. In a preferred embodiment of the invention, the substrate is heated in a plurality of steps to a predetermined temperature in a furnace divided into one or more temperature portions. Preferably, the substrate of the present invention is gradually transferred from the portion to the next portion and the residence time in each portion is the same. The substrate residence time in the present invention may be from 20 to 200 seconds, preferably from 4 to 8 seconds, more preferably from 50 to 70 seconds, and most preferably from 60 seconds. 201038769 This: The heating segmentation of the medium-sized substrate can be heated from room temperature to, for example, too: the final temperature of the war is (4), which does not need to be exceeded. The inventive substrate can then be cooled to room temperature in at least a step. The present invention prepares the desired oxygen element vapor to cause the metal precursor film to be coated with at least one layer of the rolling element film before entering the furnace. The oxygen element film on the substrate of the present invention is converted into a furnace in a furnace, and is completely evaporated in the furnace. , u in : hair: when the oxygen film of the oxygen is thicker, the oxygen element can be only partially steamed, and the metal precursor film can be converted into a partially oxygenated element. Preferably, the film of the coating group element can be distilled by the oxygen element to be == on the precursor film. It can be rapidly passed through the substrate under atmospheric conditions. The rapid evaporation of oxygen elements from the substrate causes the oxygen elements to move along the furnace m. This will result in local oxygen deficiency at the end of the final temperature', so that the local metal precursor is not completely converted into half. The exhaust gas recovery of the present invention is in addition to reducing the oxygen element of the input, and for the oxygen element concentration in the furnace chamber. Positive role. When the oxygen element film is thin, the oxygen source is input from the material source. 1 It can be 'flat' and has sufficient oxygen elemental inversion, and can be applied to the oxygen-free group element film on the substrate. 201038769 * When the substrate is coated with a layer of oxygen element film in advance, an oxygen vapor source may be introduced into the furnace chamber by an external steam source, or an internal vapor source may be disposed inside the furnace chamber. Another feature of this month is that metal precursors are produced by successive sputtering of copper/gallium and steel. To this end, a substrate made of, for example, glass can be first (four) keyed with a *: after the factory is vacuum-sputtered a second layer of copper/gallium thinner from a copper/gallium target. The third layer of indium film. The coating of molybdenum is carried out in a sputtering apparatus, and the copper/gallium and indium vehicles are carried out in a second sputtering apparatus. The substrate is then heated to convert the metal precursor preferably in the absence of oxygen and hydrogen, or only a minimum amount of oxygen and hydrogen partial pressure. The present invention can be achieved by the apparatus of the present invention. The apparatus of the present invention comprises a furnace having a chamber inlet, a substrate gate, a gas gate at the inlet of the earth plate, and a gas gate at the outlet of the substrate; - the base gas is evacuated /, and the exhaust gas channel exiting the exhaust gas channel of the oxygen element vapor/carrier gas mixture is provided with a flow distributor and/or a recovery device which allows the oxygen element not used in the reaction to be Recycled to the furnace chamber. Preferably, a recovery passage is provided between the flow distributor and the furnace chamber. The oxygen element in the present invention is preferably selenium. In the invention, the gas gate can utilize a suitable air flow to separate the gas ring brothers on both sides of the opening σ without having to set the door at the opening. In a preferred design of the invention, the air flow on both sides of the gas gate can be separately adjusted separately. It is also preferable that the furnace chamber gas gate of the present invention can be composed of at least two air curtains, and an air suction device is added between the air curtains. The shielding gas/carrier gas in the present invention is preferably an inert gas, nitrogen. The substrate inlet, substrate exit and gas door of the present invention allow the apparatus to perform a continuous pass at atmospheric pressure and defined residual gas conditions. It is preferred to carry out the continuous passage method under anaerobic conditions. In the present invention, the transport means and the inlet and outlet allow the substrate to enter the furnace, pass through the furnace chamber, and then transform the metal precursor into a semiconductor film. In the preferred embodiment, the 'oxygen element vapor/carrier gas The mixture is discarded and the passage is sent to a flow distributor which is divided into two adjustable air knives. The second exhaust gas is recovered into the furnace chamber, preferably to the open end of the furnace chamber. The second exhaust gas split passage of the present invention is discharged. That is, the remaining exhaust gas, which is left by the exhaust gas, can be filtered and then discharged. The discarded oxygen elements need to be removed or reused. In the present invention, in the preferred embodiment, the quantity dispenser can be connected to the assembly of the recovery unit 2 to the recovery unit. The recovery unit extracts the oxygen component contained in the second exhaust gas, (remaining waste), and is incorporated into the first exhaust gas: the stream. Therefore, the gas recovered into the furnace chamber increases the amount of the oxygen group element. The remaining exhaust gas that is discharged A therefore contains a lower oxygen elemental inequality, so the waste gas U is less. „Improved the oxygen content of the wealth. 201038769 In a preferred embodiment of the apparatus of the invention, the temperature of one or more walls inside the furnace chamber, the flow distributor, the recovery unit, the exhaust gas passage and the recovery passage is set and maintained It is higher than the condensation temperature of the oxygen element. This prevents the oxygen group from condensing on the inner wall and adhering thereto. It causes loss of oxygen element and troublesome maintenance. The wall temperature of the device of the present invention does not need to be the same, especially In the furnace chamber, the furnace chamber of the present invention can be divided into a plurality of sections, such as different temperature portions. _0 The temperature of the furnace chamber, the flow distributor, the recovery device, the exhaust gas passage and the inner wall of the recovery passage and the different temperature portions can be utilized. A heating and cooling system is separately and separately adjusted. In a preferred design of the invention, the segments are insulated from one another so that adjacent portions can be heated to different temperatures. The furnace of the invention can be integrated and/or segments In the preferred embodiment of the present invention, the wall of the furnace chamber is made of graphite. The conveying tool in the furnace chamber divided into a plurality of stages is preferably All the substrates in the furnace chamber are transported to the next stage step by step and the same. In the present invention, since the substrate is gradually and simultaneously transported to the next stage, the residence time of the substrate in each stage is the same, for example, 60 seconds. The invention is to improve the oxygen-free and hydrogen in the furnace chamber, and the furnace chamber can be covered by a casing, which preferably has a substrate inlet and a substrate outlet. The casing of the invention is preferably made of high-grade steel. A separate housing suction device that can be flushed by a protective gas. 201038769 In a preferred embodiment of the invention, the housing has a separate cooling system. Such heat can be removed from the furnace chamber. Preferably, the sensor housing is provided with a sensor for detecting gas and/or gas/agronomy, more preferably an oxygen sensor and/or a ^2 § 6 sensor. The oxygen sensing of the present invention The device can detect oxygen entering between the housing and the furnace chamber. The H2Se sensor of the present invention functions to ensure safety, and can be promptly found in the occurrence of hydrogenation of selenium to provide a warning. The present invention will be described in detail below with reference to the accompanying drawings. An embodiment. FIG. 1 shows a furnace chamber. It has an exhaust passage 7. The exhaust passage 7 is provided with a flow distributor 2 and a recovery device 3. The flow distributor 2 and the recovery device 3 are integrated into one unit. A recovery passage 8 is extended from the flow distributor 2 to the furnace ^1. And connecting the open end of the furnace chamber 1. The recovery device 3 is connected to a residual exhaust gas passage 9 for discharging the remaining exhaust gas. The furnace chamber i is provided with a population side and an outlet side gas door 4. The furnace chamber i is provided with a - conveying device 1Q' It has a plurality of transport rollers arranged one behind the other. The transfer device _ is used to pass the substrate u through the furnace. The furnace chamber is divided into a plurality of sections, which are independently temperature controlled and thermally isolated from each other. For clarity, 'the various parts are not shown separately, the furnace chamber i in the figure is shortened compared to the actual device length, and the middle portion of the wall is shown in broken lines. Nitrogen In the present embodiment, the shielding gas/carrier gas of the process performed by the apparatus is shown as a gas gate 4. The multi-stage air curtains each comprise (d) side-by-side air curtain flow inlets 5, each of which produces a 对~ from the top of the " . The middle portion of the gate produces a low overpressure, 匕 and a suction device, which is constructed in the upper and lower directions from the outlet 6 between the inlets of the two nitrogen gas streams. The device allows the airflow on both sides of the air curtain to be independently adjusted independently. The air curtain allows the substrate to pass through the furnace in a continuous pass at atmospheric pressure and under defined residual gas conditions, particularly oxygen free. In the present embodiment, the wall of the furnace chamber 1 is made of graphite and is covered by a high-grade steel casing, not shown, which has a separate suction means and is flushed by nitrogen. In this embodiment, a different temperature can be set in the furnace chamber by means of a heating and/or cooling system. The substrate u coated with the copper/gallium, indium and tantalum layers in this embodiment can be introduced into the furnace chamber by the inlet side gas gate 4 by the transport device 10. The substrate "passes through the portions of the furnace chamber 1 from this point and finally exits from the outlet side gas gate 4 at the end of the furnace chamber i. In this embodiment, the residence time of each portion of the process chamber of the apparatus is 60 seconds. ^ At the beginning of the furnace chamber 1, the selenium on the substrate 11 begins to melt, which is a thinner __ can be fully evaporated. The code vapor is mixed with nitrogen to form a 砸 vapor/carrier gas mixture. The mixture can be used inside the furnace. The air flow control is transported to the exhaust gas passage 7 through the furnace chamber 丨 away from the substrate 11 in the apparatus. The air flow is transported in the opposite direction. When the oxygen element thin film is thick, the oxygen element may be partially evaporated only. The metal precursor film is transformed by the molten oxygen element. The gas flow on both sides of the gas gate 4 and the exhaust gas passage 7 can be separately separated and soiled. The air flow in the furnace chamber 1 is 5± ^ ^ ^ the main waste milk passage 7 The speed needs to match the conveying speed of the substrate 11 201038769, so that when the reaction temperature is reached, there is an excess of the Kansai convertible metal precursor film into a CIGS film. The unused station is discharged through the exhaust passage 7. The exhaust passage 7 will Stone steaming The gas/carrier gas mixture is delivered to the flow distributor 2. The flow distributor 2 divides the exhaust gas into two adjustable exhaust gas splits. The first exhaust gas is split and recovered through the recovery passage 8 and flows into the open end of the furnace chamber 1. Recovery device 3 At the same time, a part of the oxygen element oxide contained in the second exhaust gas stream is extracted and incorporated into the first exhaust gas split. The remaining part of the second exhaust gas split, that is, the remaining exhaust gas, contains only a small amount of oxygen element oxide. The remaining exhaust gas is filtered and discharged through the remaining exhaust gas passage 9 to be removed or recycled for reuse. This recovery reduces the loss of selenium, thereby reducing the amount of selenium. [Fig. 1 is a device of the present invention] Figure 2 is a partial view of the apparatus of the present invention, that is, the gas door used in the embodiment [main element symbol description] 1 furnace chamber 2 flow distributor 3 recovery device 4 gas gate 5 into σ 6 flow outlet 12 201038769 7 Exhaust gas channel 8 Recovery channel 9 Residual exhaust gas channel 10 Conveyor 11 substrate

Claims (1)

201038769 七、申請專利範圍： 1 · 一種將一基板（11)上之金屬先驅物薄膜熱轉變成半 導體薄膜之方法’包含：至少塗佈一層金屬先驅物薄膜之 基板（11)在一爐中之大氣壓力環境下，被加熱至4〇〇它至 600 C之終溫度，並在一載氣與氧族元素蒸氣之混合物中被 轉變成’其巾―部份未被制於反應之該氧族 元素蒸氣被回收到製程中。 、2•如中請專利範圍帛1項之方法’其中該基板（11)在 刀成或夕個溫度部份的爐中被以多個步驟加熱至一預 設溫度。 … 3. 如申請專利範圍第2項之方法，其中該爐中之該基 板（⑴被同時逐步由—部份輸送至下—部份，在每一部份 中的停留時間相同。 4. 如申請專利範圍第3項之方法，其中停留時間可為 20至200秒’較佳為4〇至8〇秒更佳為％至7〇秒。 士申叫專利範圍第丨至4項中任一項之方法，其中 :玄基板（11)在進人該爐内之前先至少被塗佈—層氧族元素 ί產膜。 · 6·如申請專利範圍第丄至5項中任一項之方法，其中， 由外部的洛氣源將氧族元素蒸氣輸入該爐 該爐室⑴内部設-内部的蒸氣源。 種將—基板（11)上之金Μ驅物薄膜熱轉變成半 導體溥膜之裝罾，坌— 置，、包括.一爐，其爐室（1)具有一基板（11) 入口及一基板（U)出 一 在s玄基板（11)入口及在該基板 !4 201038769 (⑴出口的氣體閘門(4)、一基板輸送工具⑽、以及一將 廢氣排出爐室⑴之廢氣通道⑺，該處設有一將廢氣分成兩 股氣流之流量分配器（2)，及一回收通道⑻，其將第一廢氣 分流回收至該爐室（1)中。 8·如申專利範圍第7項之裝置，其中該回收通道⑻ 連接到該爐室開端部。 9. 如申請專利範圍第7 < 8項之裝置，其中該流量分 〇 配益⑺與一回收裝置（3)連接，或為一回收裝置之組件，該 回收裝置將第二廢氣分流（剩餘廢棄）中所含的氧族元素 抽出，而併入第一廢氣分流中，故回收回該爐室的氣體提 尚了氧族元素的量。 10. 如申請專利範圍第7至9項中任一項之裝置，其中 該爐室（1)及/或該廢氣通道（7)及/或該流量分配器（2)及/ 或邊回收裝置（3)及/或該回收通道（8)的該壁溫被控制。 Π.如申请專利範圍第7至1〇項中任一項之裝置，其 0 中，該爐室（1)可分成多段接續的不同溫度部份。 12. 如申請專利範圍第u項之裝置，其中各段彼此隔 熱。 13. 如申請專利範圍第7至12項中任一項之裝置，其 中該爐室（1)整體及/或各段分別隔熱。 14. 如申請專利範圍第7至13項中任一項之裝置，其中， 該爐室（1)中設有一偵測氣體及/或氣體濃度之感測器。 八、圖式（請見下頁）：201038769 VII. Patent Application Range: 1 · A method for thermally converting a metal precursor film on a substrate (11) into a semiconductor film 'includes: a substrate (11) coated with at least one metal precursor film in a furnace Under atmospheric pressure, it is heated to a temperature of 4 〇〇 to 600 C, and is converted into a mixture of carrier gas and oxygen elemental vapor into a portion of the oxygen that is not reacted. The elemental vapor is recycled to the process. 2. The method of claim 1 wherein the substrate (11) is heated to a predetermined temperature in a plurality of steps in a furnace or a temperature portion of the furnace. 3. The method of claim 2, wherein the substrate in the furnace ((1) is gradually transferred from the portion to the lower portion, the residence time in each portion is the same. 4. The method of claim 3, wherein the residence time may be 20 to 200 seconds, preferably 4 to 8 seconds, more preferably from 7 to 7. The term is patented to any of the fourth to fourth patents. The method of the present invention, wherein: the substrate (11) is at least coated with a layer of oxygen element 355 before being introduced into the furnace. 6. The method of any one of claims 5 to 5 Wherein, the oxygen elemental vapor is supplied from the external gas source to the internal vapor source of the furnace chamber (1). The metal film of the substrate is electrically converted into a semiconductor film. Mounting, 坌-, including, a furnace, the furnace chamber (1) has a substrate (11) inlet and a substrate (U) out at the entrance of the s-substrate (11) and on the substrate! 4 201038769 ( (1) an outlet gas gate (4), a substrate transfer tool (10), and an exhaust passage (7) for exhausting the exhaust gas to the furnace chamber (1), There is provided a flow distributor (2) for dividing the exhaust gas into two air flows, and a recovery passage (8) for collecting the first exhaust gas to the furnace chamber (1). 8. The device of claim 7 of the patent scope, Wherein the recovery passage (8) is connected to the open end of the furnace chamber. 9. The apparatus of claim 7th, wherein the flow distribution benefit (7) is connected to a recovery device (3) or is a recovery device. In the assembly, the recovery device extracts the oxygen group element contained in the second exhaust gas split (remaining waste) into the first exhaust gas split, so that the gas recovered back to the furnace chamber raises the amount of the oxygen group element. 10. The device of any one of claims 7 to 9, wherein the furnace chamber (1) and/or the exhaust gas passage (7) and/or the flow distributor (2) and/or the side recovery device (3) and/or the wall temperature of the recovery passage (8) is controlled. 装置. The apparatus of any one of claims 7 to 1 wherein the furnace chamber (1) is divided into Multi-section continuous temperature parts 12. As in the device of the scope of application of the scope of paragraph u, the sections are insulated from each other 13. The device of any one of claims 7 to 12, wherein the furnace chamber (1) is thermally insulated as a whole and/or each segment. 14. As claimed in any of claims 7 to 13 The device of the item, wherein the furnace chamber (1) is provided with a sensor for detecting gas and/or gas concentration. 8. Drawing (see next page):
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