201134950 六、發明說明： 【發明所屬之技術領域】 本發明係關於水反應性鋁複合材料、水反應性鋁膜、 該錦膜之製造方法、及成膜室用構成構件，特別是關於使 用添加有欽之銘的水反應性纟g複合材料、該水反應性銘複 合材料所構成之水反應性鋁膜、該鋁膜之製造方法、及以 該鋁膜所被覆之成膜室用構成構件。 【先前技術】 用以藉濺鍍法、真空蒸鍍法、離子沉積法、CVD法等 形成薄膜的成膜裝置中，於該裝置內所設置之成膜室用構 成構件，於成膜製程中不可避免地會附著成膜材料所構成 金屬或金屬化合物之膜。該成膜室用構成構件，可舉例如 ’用以防止膜附著於基板以外之真空容器內部的防止附著 板、開關器 '用以使其僅成膜於基板之既定部位之遮罩、 或基板運送用輸送盤等。於成膜製程中，於該等構件亦會 附著與目的物薄膜（應形成於基板上之薄膜）相同組成之 膜。該等構件通常係於除膜附著膜後重覆使用。 不可避免地附著於該等成膜室用構成構件之膜，隨成 膜製程之作業時間的長度而增厚。如此之附著膜，因其之 內部應力或反覆之熱歷程所致之應力變成顆粒而由成膜室 用構成構件剝離，並附著於基板，而成爲產生膜缺陷的原 因。因此，成膜室用構成構件，於附著膜未產生剝離的階 段，係定期地進行由成膜裝置取出，洗淨以除去附著膜， -5- 201134950 之後進行表面精加工而再使用的循環。 成膜材料，當使用例如鋁、鉬、鈷、鎢、鈀、_、銦 、鈦、銶、鉅、金、鉑、硒、銀等有價金屬時，要求其能 確立將未於基板上形成膜而附著於基板以外之構成構件的 金屬回收、並使構成構件再利用的處理技術。 例如，當爲成膜裝置中爲了防止成膜材料附著於基板 以外之裝置內壁或各成膜室用構成構件表面等所使用之防 止附著板時，目前的狀況是將成膜時所附著之附著物除膜 而再利用。該附著物之除膜法，一般係進行噴砂法、以酸 或鹼之濕式蝕刻法、以過氧化氫等之利用氫脆性之除膜法 、以及利用電解之除膜法。於該情況下，於實施附著物之 除膜處理之際，由於防止附著板亦會些許溶解而受到損傷 ，故再利用次數有限。因此，期盼開發一種能夠儘可能減 少防止附著板之損傷的除膜法。 上述噴砂法中所產生之砂屑、酸或鹼處理等之藥液處 理中所產生之廢液中之所除膜之附著膜的濃度若低，有價 金屬之回收費用增高，不划算。如此之情形，目前的狀況 是作爲廢棄物處理。 上述藥液處理，不僅藥液本身之費用高，使用完之藥 液之處理費用亦高，且由防止環境汙染的觀點，亦希望藥 液的使用量能盡量減少。再者，所進行如上述之藥液處理 ，由防止附著板所除膜之成膜材料會變質成新的化學物質 ，欲由所除膜之附著物僅回收成膜材料，會使費用再增加 。因此，目前的狀況是僅符合回收成本之單價的成膜材料 -6- 201134950 爲回收對象。 除上述之附著物之除膜法以外，已知有下述技術，於 具備以水反應性鋁複合材料（具有可於水分存在之環境氣 氛中反應而溶解之性質）所構成之鋁膜被覆之構成構件的 裝置內實施成膜製程，藉鋁膜之反應、溶解將成膜中所附 著之膜除膜、分離’而由該所除膜之附著膜將成膜材料之 有價金屬回收的技術（例如，參照專利文獻1 )。該水反 應性鋁複合材料，係由鋁或鋁合金與銦、錫、銦與錫、或 該等之合金所構成。 專利文獻1 :曰本特開2005-2 5 6063號公報（申請專利 範圍） 【發明內容】 〔發明欲解決之課題〕 本發明之課題在於解決上述之以往技術之問題點，而 提供一種使用2N〜5N鋁之可於水分存在之環境氣氛中反 應而溶解之鋁複合材料、該鋁複合材料所構成之鋁膜、該 鋁膜之製造方法、及以該鋁膜所被覆之成膜室用構成構件 〔解決課題之手段〕 本發明之水反應性鋁複合材料，其特徵係，於選自2 N 鋁〜5 N鋁之鋁’以鋁基準’添加2 · 〇〜5.0 w t %之銦、以及 0.05〜l.Owt%之選自鈦、釩及锆之金屬所成。 201134950 由於鋁複合材料具有如此之組成，由該材料所得之銘 膜’與鋁中之雜質銅之量沒有關係，於水分存在之環境氣 氛中容易產生氫而溶解。 於上述水反應性鋁複合材料所構成之鋁熔射膜，若銦 的添加量未滿2 . Owt%，則與水分的反應性降低，而若超過 5 .Owt%，則與水分的反應性非常高，而會與大氣中的水分 反應’又，自鈦、釩及锆之金屬的添加量若未滿〇.05 wt% ，則與未添加金屬的情形相同，無法得到所欲之效果，而 若超過1 · 0 w t %，則由鋁複合材料以熔射所得之鋁膜變硬， 目的之水反應性、亦即水的溶解性降低。 本發明之水反應性鋁膜，其特徵係由上述水反應性鋁 複合材料所構成。 本發明之水反應性鋁膜之製造方法，其特徵係，於選 自2N鋁〜5N鋁之鋁，以鋁基準，添加2.0〜5.0wt%之銦、 以及0.05〜l.Owt%之選自鈦、釩及锆之金屬，以使組成均 勻的方式使上述材料熔融，將該熔融材料對基材表面熔射 並急速冷卻凝固，藉此進行成膜。 本發明之成膜室用構成構件，其特徵係，於表面具備 上述水反應性鋁複合材料所構成水反應性鋁膜、或藉上述 水反應性鋁膜之方法所製造之水反應性鋁膜。 上述構成構件，其特徵係防止附著板、開關器或遮罩 〔發明的效果〕 -8 - 201134950 本發明之水反應性鋁複合材料所構成之鋁膜，可藉熔 射等簡單之製程容易地以廉價的成本製造。該鋁膜，可達 到以下效果，於再經過以3 0 0〜3 5 0 °C左右之高溫之成膜製 程中之熱歷程後，與鋁中之雜質銅之量沒有關係，亦具備 可於水分存在之環境氣氛中反應而溶解的性質。 本發明之鋁膜，於水分的存在下邊產生氫而有效率地 溶解，故若使用具備以該水反應性鋁膜被覆之成膜室用構 成構件（例如，防止附著板、開關器或遮罩等）之成膜裝 置進行成膜，則可將成膜製程中附著於防止附著板等表面 之成膜材料所構成之不可避免的附著膜，藉該鋁膜之反應 、溶解來除膜、分離，並由該所除膜之附著膜可容易地回 收成膜材料之有價金屬，又，由於於除膜、分離之際，大 致不會對構成構件造成損傷，故具有大幅增加其之再利用 次數的效果。 【實施方式】 當使用成膜裝置以濺鍍法等各種成膜方法製造薄膜時 ，成膜室內會因製程溫度受到反覆之熱歷程。因此，利用 本發明之水反應性鋁複合材料所構成之鋁膜而欲將成膜室 內不可避免地附著之膜除膜時，以鋁膜被覆之防止附著板 等設置於成膜室內之構成構件之表面亦受到反覆之熱歷程 。因此，受到熱歷程前之熔射（電弧熔射、火焰噴射）成 膜時之鋁膜，必須安定而容易處理，並且，成膜製程中經 熱歷程後之不可避免地附著有附著膜之鋁膜，須具有容易 -9 - 201134950 地由基材除膜之溶解性（活性）、且安定。當爲本發明之 水反應性鋁膜時，可充分滿足如此之溶解性。 上述成膜室內之熱歷程之上限溫度，例如，當以濺鍍 法 '真空蒸鍍法、離子沉積法、CVD法等成膜時，爲300 〜3 50 °C，故一般只要經3 00°C之熱歷程後之鋁膜爲具有水 反應性者，於實用上即足夠，較佳爲，經350 °C之熱歷程 後之鋁膜爲具有水反應性者。 關於上述之熔射膜溶解性，係以將鋁膜被覆之基材浸 漬於既定溫度（40〜130 °C、較佳爲80〜100 °C)之溫水（ 較佳爲去離子水）既定時間後之液中的電流密度（於本發 明，稱爲溶解電流密度（mA/ cm2 ))來評價。該測定方 法，係測定樣品之處理液浸潰前後之質量減少，由表面積 、浸漬處理時間等換算成電流密度之値的方法。以該方法 所測定之溶解電流密度，若爲50 mA/ cm2以上，則經成膜 製程之熱歷程後之不可避免地附著有附著膜之鋁膜，可謂 具有能容易地由基材將各附著膜除膜之溶解性（活性）。 本發明人等，於探討經熱歷程後之各種鋁熔射膜之溶 解性的過程中發現，依存於鋁中所存在之雜質銅之量，鋁 膜之溶解性會變動，而藉由於鋁-銦系中添加既定量之選 自鈦、釩及锆之金屬，可改良其之溶解性。亦即，藉由於 選自2N鋁〜5N鋁之鋁，以鋁基準，添加2.0〜5.0wt%之銦 、以及〇·〇5〜1.0wt%(較佳爲〇·1〜l.〇wt%、更佳爲0.13〜 〇.6wt% )之選自鈦、釩及锆之金屬所成之水溶性鋁複合材 料所得到之鋁膜，可於與鋁中之雜質銅之量沒有關係之下 -10 - 201134950 達成所欲之目的。選自鈦、釩及鍩之金 0.05 wt%、或超過1 .〇wt%，則會產生上 金屬之添加量爲0. 1 w t %者之水之溶解也 又，0.9wt%者較l.Owt%者所得之鋁膜較 高。 於本發明，對於純度2 N ( 9 9 % )、 (9 9.99%)及 5 N ( 9 9.9 9 9 % )之鋁爲有 5N鋁，例如，可藉將電解法所得之2N 9 9 · 9 % )鋁再以3層電解法，或利用部分 所致之凝固時之固相與液相之溫度差之 等鋁中之主要雜質爲鐵、矽，其他亦含 其之含量係隨鋁原料之產地等而不同。 由本發明之水反應性鋁複合材料所 2N鋁〜5N鋁中均勻、高度地分散有銦 之金屬，故與存在於鋁中之雜質銅之量 在有水、水蒸氣、水溶液等之水分的環 應而溶解。 一般而言，於鋁-銦系中，鋁與銦 位差非常大，但若存在有鋁之自然氧化 化。然而，一旦自然氧化膜破裂，若與 之電位差會急劇地促進鋁之離子化。此 學變化，會以原本之狀態高度分散存在 於銦爲低熔點且不會與鋁固熔體化，故 之密度差，將以使鋁與銦組成均勻的方 屬的添加量若未滿 述問題。又，該等 i較0.05wt%者闻， 硬、水之溶解性較 3 N ( 9 9.9%) ' 4N 玫。其中，4N鋁及 (9 9%)鋁、3 N ( 凝固法（偏析法） 方法等而製得。該 有銅、鎳、碳等， 構成之鋁膜，係於 與選自鈦、釩及锆 沒有關係，可於存 境氣氛中容易地反 之間之電氣化學電 膜，則鋁不會離子 銦直接鍵結，則其 時，銦不會進行化 於鋁結晶粒中。由 若持續注意鋁與銦 式熔融之材料，以 -11 - 201134950 熔射法對基材進行熔射，藉急速冷卻凝固與其之壓縮效果 則可得所欲之鋁膜。 與該情形同樣的，若將以使鋁與銦與選自鈦、釩及銷 之金屬以組成均勻的方式熔融之材料，以熔射法對基材進 行熔射，藉急速冷卻凝固與其之壓縮效果則可得本發明之 鋁膜。 所添加之銦與選自鈦、釩及锆之金屬’係藉熔射製程 高度分散於鋁結晶粒中，保持與鋁直接接觸的狀態。由於 銦（鈦、釩、銷）無法與鋁作成安定層，故鋁/銦（鈦、 釩、錐）界面保持高能量，而於水分存在之環境氣氛中於 與水分之接觸面激烈地反應。又，添加元素之銦與自鈦、 釩及鉻之金屬爲高度之分散狀態，此外，由於所產生之H2 氣泡之膨脹所致之機械作用，以AlOOH爲主體之反應生成 物不會於表面皮膜化而微粉化散布至液中，而溶解反應於 陸續更新之反應界面持續地、急遽地進行。 如上述之鋁-銦-選自鈦、釩及锆之金屬系的舉動， 與鋁純度沒有關係，於2N鋁〜5N鋁中皆同樣的產生。 又，爲鋁-銦系的情況下，依存於鋁中所存在之雜質 銅之含量，對經熱歷程後之鋁熔射膜之溶解性所造成之影 響大。若銅含量多（例如，40ppm )，則經高溫之熱歷程 後之鋁熔射膜之溶解性差，於附著膜之除膜處理之際，即 使提高水的溫度亦難以除膜。又，當銅含量低（例如， 1 Oppm )時，必須提高用以附著膜之除膜處理之水的溫度 (例如，1 00°C以上）。然而，藉由於鋁一銦系添加既定 -12- 201134950 量之選自鈦、釩及鉻之金屬，可於與銅含量沒有關係之下 顯示所欲之溶解性。 以下，主要係說明4N鋁-銦一鈦所構成之水反應性鋁 複合材料之例。鋁熔射膜，係使用銦與鈦同樣地分散於4N 鋁中之鋁-銦-鈦複合材料，以熔射法於既定之環境氣氛 中成膜於被處理基材之表面，藉此來製造。所得之鋁-銦 一鈦熔射膜，於鋁結晶粒中，係以均勻且高度分散之狀態 含有銦及鈦之結晶粒（粒徑1 Onm以下）。 上述鋁熔射膜，例如係以如下方式製造。準備4N鋁、 銦及鈦，對鋁，配合2.0〜5.0wt%之銦、及0.05〜1 .Owt% ( 較佳爲0 · 1〜1.0 w t %、更佳爲0.1 3〜0.6 w t % )之鈦，使銦及 鈦均勻熔解於鋁中，將加工成棒狀或線形狀之物作爲熔射 材料使用，例如藉由熔射法，於空氣中，以周知之熔射條 件’噴附於成爲成膜裝置之防止附著板等之成膜室用構成 構件之基材之表面，並使其急速冷卻而被覆，藉此，可製 造具備所欲之水反應性鋁熔射膜之基材。如此所得之鋁熔 射膜，如上述，係銦及鈦以高度分散之狀態存在於鋁結晶 粒中之膜。 將如上述以鋁熔射膜被覆之基材浸漬於溫水中、或吹 附水蒸氣，則例如當浸漬於既定溫度之溫水中時，由開始 浸漬後反應即開始’產生氫氣’且若反應持續進行則由於 析出之銦等使水黑色化，最終，由於熔射膜與水之激烈反 應而微粉化而全部溶解’於溫水中鋁、銦、鈦（釩、锆） 等沉澱而殘留。該反應，水溫愈高反應愈激烈。 -13- 201134950 上述熔射膜，係以使用棒狀或線形狀之材料之以火焰 噴射所形成的例進行說明，而使用粉末狀之材料之火焰噴 射亦可，且電弧熔射、電漿噴敷亦可。於本發明，係依據 該等熔射法，以周知之製程條件，將上述原材料熔融，吹 付至基材表面使其急速冷卻凝固，而形成熔射膜。 如上述，作爲成膜裝置之成膜室內所設置之防止附著 板或遮罩等成膜室用構成構件，只要使用以本發明之水反 應性鋁膜被覆其之表面者，於既定次數之成膜製程後，可 簡單地由不可避免地附著有成膜材料之成膜室用構成構件 ，將該附著膜除膜，而能容易地回收有價金屬。 於該情形，剝離處理液，非使用化學藥品，而係單純 地使用純水等水、水蒸氣、或水溶液，故可避免防止附著 板等成膜室用構成構件因溶解所受到的損傷，而該等之再 利用次數與使用藥品的情形相比有大幅地增加。又，由於 未使用藥品，以可大幅削減處理成本並達到環境保護。再 者’由於附著於防止附著板等成膜室用構成構件的大部分 成膜材料不溶解於水，故能將與成膜材料相同組成者以相 同型態之固體直接回收，是其優點。再者，不僅回收成本 巨幅下降’回收步驟亦簡單化，故以具有可回收材料之範 圍增廣的優點。例如，當成膜材料爲貴重金屬或稀有金屬 等高價金屬時，若將本發明之水反應性鋁複合材料所構成 之熔射膜使用於防止附著板等成膜室用構成構件，則藉由 將具有成膜中不可避免地附著之膜之成膜室用構成構件浸 漬於水中或吹付水蒸氣，即可將成膜材料所構成之附著膜 -14 - 201134950 除膜，故可不造成污染地將貴重金屬或稀有金屬回收。回 收成本廉價、且可以高品質回收成膜材料。 以下，根據參考例及實施例詳細地說明本發明。 (參考例） 使用2N鋁、3N鋁及4N鋁’探討添加有銦之鋁一銦組 成中鋁純度、鋁中之雜質銅量、與所得熔射膜之溶解性的 關係。銦之添加量係銘重量基準。 (a) 2N 鋁（雜質銅：< 400ppm) -3.0wt% 銦 (b) 3N鋁（雜質銅：7〇PPm) -3.0wt%銦 (c ) 3N鋁（雜質銅：檢測界限以下）一 3 .Owt%銦 (d ) 4N鋁（雜質銅：檢測界限以下）一 3.0wt%銦 以上述比例配合鋁及銦’使用於鋁中均勻地熔解有銦 並加工成棒形狀之熔射材料’以熔棒式火焰噴射（熱源： C2H2-〇2氣體，約3000°C ) ’於大氣環境氣氛中’吹付於 鋁製基材之表面而形成熔射膜。對於如此製得之各熔射膜 ，施以常溫〜3 5 0 °C之熱處理（大氣中、1小時、爐冷）取 代成膜製程中所受到之熱歷程。將受熱處理前之狀態（常 溫）之附熔射膜基材、及經熱處理後（經熱歷程後）之附 熔射膜基材浸漬於8 〇 °C之純水3 0 0ml中’測定浸漬液之電 流密度（mA/ cm2 )以探討各熔射膜之溶解性。 關於2N鋁〜4N鋁之鋁熔射膜之溶解性的探討結果’ 發現4N鋁之雜質銅之量爲檢測界限以下時之銘溶射膜的溶 解度，較2N銘及3N鋁時高，當爲3N鋁及4N鋁之雜質銅之 -15- 201134950 量爲檢測界限以下時，熱處理溫度3 5 0 °C之溶解電流密度 爲50 mA/cm2以上，爲可溶解。然而，當爲2N鋁及3N鋁 之雜質銅之含量爲70PPm以上時，經350t之熱處理（熱歷 程）之熔射膜’不具充分之溶解性。於該情形，即使將處 理液溫度提昇爲100°C以上亦無法溶解。 又，對於4N鋁（雜質銅：30ppm ) - 2.5wt%銦及4N鋁 (雜質銅：lOppm ) - 4.0wt%銦，與上述同樣地實施的結 果，經3 5 0 °C之熱處理（熱歷程）之熔射膜亦同樣地不具 充分之溶解性。 〔實施例1〕 於本實施例，如以下，使用於4N鋁添加銦之鋁-銦、 於4N鋁添加銦及鈦之鋁_銦-鈦、以及於5N鋁添加銦之 鋁-銦，探討添加鈦之鋁-銦組成中之鋁純度、與鈦添加 之有無所致之熔射膜溶解性之關係（參照圖1 )。銦及鈦 之添加量係鋁重量基準。 (a ) 4N鋁（雜質銅：檢測界限以下）_ 3.0wt%銦一 0 _ 2 w t % 鈦 (b ) 5N鋁（雜質銅：檢測界限以下）—3.0wt%銦 (c) 4N鋁（雜質銅：檢測界限以下）-3.0wt%銦 又，如以下，使用於含有雜質鐵、矽、銅、鎳、及碳 之4N鋁添加有銦之鋁-銦’探討雜質對熔射膜溶解性所造 成之影響（參照圖2 )。銦及駄之添加量係鋁重量基準。 (a) 4N 銘（雜質銅· l〇PPm、鐵：80ppm、砂： -16- 201134950 1 OOppm ' 鎳：<10ppm) — 3.0wt%銦 (b ) ULMAT 產 4N 銘（雜質銅：40ppm、鐵：40ppm、 砂：80ppm、鎳：< lOppm) — 3.5wt°/〇 銦 (c) 4N 銘（雜質銅：lOppm、鐵：60ppm、砂：100 p p m、鎳：檢測界限以下）-3.0 w t %銦 (d ) ULMAT 產 4N 鋁（雜質銅：40ppm、鐵：llOppm 、石夕：lOOppm、鎳：< lOppm、碳：30ppm) - 3.0wt%銦 (e)中國產3N鋁（雜質銅：70ppm、鐵：120ppm、 砂· lOOppm、鎳：30ppm) - 3.0wt%銦 再者，如以下，使用於4N鋁添加銦之鋁-銦、及於 4N鋁添加銦及鈦之鋁-銦-鈦，探討添加鈦之鋁-銦組成 中之鋁中之雜質銅之含量、與鈦添加之有無所致之熔射膜 溶解性之關係（參照圖3 )。銦及鈦之添加量係鋁重量基 準。 (a ) 4 N鋁（雜質銅：檢測界限以下）—2.7 w t %銦一 0 · 2 0 w t % 多太 (b) 4N鋁（雜質銅：30ppm) ~3.〇wt%銦-0.40wt% 鈦 (c) 4N 鋁（雜質銅：40ppm) *~3.〇wt% 銦-0.56wt% 鈦 (d ) 4 N鋁（雜質銅：檢測界限以下）_ 3.0 w t %銦 (e) 4N鋁（雜質銅：30ppm) ~3.5wt%銦 (f) 4N 鋁（雜質銅·· 40ppm) ~3.〇wt% 銦[Technical Field] The present invention relates to a water-reactive aluminum composite material, a water-reactive aluminum film, a method for producing the film, and a constituent member for a film forming chamber, and particularly relates to use and addition A water-reactive 纟g composite material having a water-reactive 纟g composite material, a water-reactive aluminum film composed of the water-reactive composite material, a method for producing the aluminum film, and a constituent member for a film forming chamber covered with the aluminum film . [Prior Art] In a film forming apparatus for forming a film by a sputtering method, a vacuum deposition method, an ion deposition method, a CVD method, or the like, a constituent member for a film forming chamber provided in the device is formed in a film forming process A film of a metal or a metal compound composed of a film-forming material is inevitably attached. The constituent member for the film forming chamber may be, for example, a mask for preventing the adhesion of the film to the inside of the vacuum container other than the substrate, and a switch for forming a mask on the predetermined portion of the substrate or the substrate. Transport trays, etc. In the film forming process, the same composition as the film of the object (the film to be formed on the substrate) is adhered to the members. These members are usually used repeatedly after the film is attached to the film. The film which inevitably adheres to the constituent members for the film forming chamber is thickened in accordance with the length of the working time of the film forming process. Such an adhesive film is detached from the constituent members of the film forming chamber due to the stress caused by the internal stress or the thermal history of the coating, and adheres to the substrate, which causes the film defect. Therefore, the constituent members for the film forming chamber are periodically subjected to a cycle in which the film is removed by the film forming apparatus, and the film is removed to remove the adhered film, and the surface is finished and reused after -5 - 201134950. The film-forming material, when using a valuable metal such as aluminum, molybdenum, cobalt, tungsten, palladium, _, indium, titanium, ruthenium, giant, gold, platinum, selenium, silver, etc., is required to establish that a film will not be formed on the substrate The metal that is attached to the constituent members other than the substrate is recovered and the constituent members are reused. For example, in the film forming apparatus, in order to prevent the film forming material from adhering to the inner wall of the device other than the substrate or the film forming member for the surface of the film forming chamber, the current state of the film is attached to the film forming device. The attached matter is reused in addition to the film. The film removing method of the deposit is generally a sand blasting method, a wet etching method using an acid or an alkali, a film removing method using hydrogen embrittlement such as hydrogen peroxide, and a film removing method using electrolysis. In this case, when the film removal treatment of the deposit is carried out, since the adhesion preventing plate is slightly dissolved and damaged, the number of reuses is limited. Therefore, it is desired to develop a film removal method which can minimize the damage of the adhesion preventing plate. If the concentration of the adhered film of the removed film in the waste liquid generated by the chemical treatment such as sand, acid or alkali treatment generated in the above-described sand blasting method is low, the recovery cost of the valuable metal is increased, which is not cost-effective. In this case, the current situation is treated as waste. The above-mentioned liquid chemical treatment not only has a high cost of the liquid medicine itself, but also has a high treatment cost for the used liquid, and it is also desirable to minimize the use of the liquid medicine from the viewpoint of preventing environmental pollution. Furthermore, if the chemical liquid treatment as described above is carried out, the film forming material which prevents the film from being removed by the adhesive sheet is deteriorated into a new chemical substance, and it is necessary to recover only the film forming material from the attached matter of the removed film, which increases the cost. . Therefore, the current situation is that the film-forming material -6-201134950, which is only in accordance with the unit price of the recovery cost, is the object of recycling. In addition to the above-described film removal method of the deposit, there is known a technique in which an aluminum film having a water-reactive aluminum composite material (having a property of being soluble in an ambient atmosphere in the presence of moisture) is coated. A technique in which a film forming process is carried out in a device constituting a member, and a film of a film forming material is recovered by an adhesive film that removes film and separates the film adhered to the film by reaction of the aluminum film ( For example, refer to Patent Document 1). The water-reactive aluminum composite material is composed of aluminum or an aluminum alloy and indium, tin, indium and tin, or alloys thereof. [Patent Document 1] 曰本特开 2005-2 5 6063 (Patent Application Scope) [Disclosure] [Problem to be Solved by the Invention] An object of the present invention is to solve the above problems of the prior art and to provide a use of 2N ～5N aluminum aluminum composite material which can be reacted and dissolved in an ambient atmosphere in which water is present, an aluminum film composed of the aluminum composite material, a method for producing the aluminum film, and a film forming chamber covered with the aluminum film Component [Means for Solving the Problem] The water-reactive aluminum composite material of the present invention is characterized in that an aluminum selected from 2 N aluminum to 5 N aluminum is added with 2 · 〇 to 5.0 wt % of indium on the basis of aluminum, and 0.05 to 1.0% by weight of a metal selected from the group consisting of titanium, vanadium and zirconium. 201134950 Since the aluminum composite material has such a composition, the film "from the material" has no relationship with the amount of copper in the aluminum, and hydrogen is easily dissolved in an ambient atmosphere in which water is present. In the aluminum spray film formed of the water-reactive aluminum composite material, if the amount of indium added is less than 2.0% by weight, the reactivity with water is lowered, and if it exceeds 5.0% by weight, reactivity with moisture is obtained. Very high, and will react with the moisture in the atmosphere. - If the amount of metal added from titanium, vanadium and zirconium is less than .05 wt%, the same effect as in the case where no metal is added, the desired effect cannot be obtained. On the other hand, if it exceeds 1.0% by weight, the aluminum film obtained by the aluminum composite material is hardened, and the water reactivity of the object, that is, the solubility of water is lowered. The water-reactive aluminum film of the present invention is characterized in that it is composed of the above water-reactive aluminum composite material. The method for producing a water-reactive aluminum film according to the present invention is characterized in that it is selected from the group consisting of 2N aluminum to 5N aluminum, and is added with 2.0 to 5.0% by weight of indium and 0.05 to 1.0% by weight based on aluminum. The metal of titanium, vanadium, and zirconium is melted by so that the composition is uniform, and the molten material is melted on the surface of the substrate and rapidly cooled and solidified to form a film. The constituent member for a film forming chamber of the present invention is characterized in that the surface is provided with a water-reactive aluminum film composed of the water-reactive aluminum composite material or a water-reactive aluminum film produced by the method of the water-reactive aluminum film. . The above-mentioned constituent member is characterized in that an adhesion preventing plate, a switch or a mask is prevented [Effect of the invention] -8 - 201134950 The aluminum film composed of the water-reactive aluminum composite material of the present invention can be easily fabricated by a simple process such as spraying Made at a low cost. The aluminum film can achieve the following effects, and after the heat history in the film forming process at a high temperature of about 300 to 350 ° C, it has no relationship with the amount of copper in the aluminum, and is also available. The property of reacting and dissolving in an ambient atmosphere in which moisture exists. Since the aluminum film of the present invention is efficiently dissolved by the generation of hydrogen in the presence of moisture, a constituent member for a film forming chamber covered with the water-reactive aluminum film (for example, an adhesion preventing plate, a switch or a mask) is used. When the film forming apparatus is formed into a film, an unavoidable adhesive film which is formed by a film forming material which is adhered to a surface such as an adhesion preventing plate during the film forming process can be removed, and the film is removed and separated by reaction and dissolution of the aluminum film. And the deposited film of the film to be removed can easily recover the valuable metal of the film forming material, and since the film is not substantially damaged when the film is removed or separated, the number of reuses is greatly increased. Effect. [Embodiment] When a film is produced by various film forming methods such as a sputtering method using a film forming apparatus, the film forming chamber is subjected to a heat history which is repeated due to the process temperature. Therefore, when the film which is inevitably attached to the film forming chamber is removed by the aluminum film formed of the water-reactive aluminum composite material of the present invention, the member which is placed in the film forming chamber by the aluminum film is prevented from being attached to the film forming chamber. The surface is also subject to repeated heat history. Therefore, the aluminum film which is formed by the filming (arc jet, flame spray) before the heat history must be stable and easy to handle, and the aluminum attached to the film inevitably adheres to the film forming process after the heat history. The film must have a solubility (activity) which is easily removed from the substrate by the -9 - 201134950, and is stable. When it is the water-reactive aluminum film of the present invention, such solubility can be sufficiently satisfied. The upper limit temperature of the thermal history in the film formation chamber is, for example, 300 to 3 50 ° C when formed by a sputtering method, a vacuum deposition method, an ion deposition method, a CVD method, or the like, so that it is generally 300°°. The aluminum film after the thermal history of C is water-reactive, and is practically sufficient. Preferably, the aluminum film after heat history at 350 ° C is water-reactive. The above-mentioned melt film solubility is determined by immersing the base material coated with the aluminum film at a predetermined temperature (40 to 130 ° C, preferably 80 to 100 ° C) in warm water (preferably deionized water). The current density in the liquid after the time (in the present invention, referred to as dissolved current density (mA/cm2)) was evaluated. This measurement method is a method in which the mass of the sample before and after the treatment liquid is reduced, and the surface area, the immersion treatment time, and the like are converted into a current density. When the dissolved current density measured by the method is 50 mA/cm2 or more, the aluminum film adhering to the film inevitably adheres to the thermal history of the film forming process, and it can be easily attached from the substrate. The solubility (activity) of the membrane in addition to the membrane. The present inventors have found that in the process of studying the solubility of various aluminum spray films after the thermal history, the solubility of the aluminum film varies depending on the amount of the impurity copper present in the aluminum, and the aluminum- A metal selected from the group consisting of titanium, vanadium, and zirconium is added to the indium system to improve the solubility thereof. That is, by using aluminum selected from 2N aluminum to 5N aluminum, 2.0 to 5.0 wt% of indium, and 〇·〇 5 to 1.0 wt% (preferably 〇·1 to l.〇wt%) are added on an aluminum basis. More preferably, the aluminum film obtained from the water-soluble aluminum composite material selected from the metals of titanium, vanadium and zirconium is not related to the amount of impurity copper in the aluminum- 10 - 201134950 Achieve the desired purpose. The weight of the gold added to the titanium, vanadium and niobium is 0.05 wt%, or more than 1. 〇wt%, the amount of the upper metal added is 0.1%, and the dissolution of the water is also 0.9% by weight. The aluminum film obtained by Owt% is higher. In the present invention, aluminum having a purity of 2 N (99%), (99.99%), and 5 N (99.99.9%) is 5N aluminum, for example, 2N 9 9 · 9 obtained by electrolysis %) aluminum is further composed of three layers of electrolysis, or the main impurities in the aluminum which are partially separated by the temperature difference between the solid phase and the liquid phase, and the other impurities are also contained in the aluminum raw material. The origin is different. In the water-reactive aluminum composite material of the present invention, the metal of indium is uniformly and highly dispersed in 2N aluminum to 5N aluminum, so that the amount of copper present in the aluminum is in the ring of water such as water, water vapor or aqueous solution. It should dissolve. In general, in the aluminum-indium system, the difference between aluminum and indium is very large, but if there is natural oxidation of aluminum. However, once the natural oxide film is broken, if it is inferior to the potential, the ionization of aluminum is sharply promoted. This change in the state will be highly dispersed in the original state in which indium is a low melting point and does not melt with aluminum, so the density difference will be such that the addition amount of aluminum and indium is uniform. problem. Moreover, these i are more than 0.05% by weight, and the solubility in hard and water is 3 N (9 9.9%) '4N rose. Among them, 4N aluminum and (9 9%) aluminum, 3 N (solidification method (segregation method) method, etc.. The copper film, such as copper, nickel, carbon, etc., is selected from titanium and vanadium. Zirconium has no relationship, and can be easily reversed between the electrochemical atmospheres in the atmosphere. If aluminum is not directly bonded to the indium, then the indium will not be converted into the aluminum crystal grains. With the indium-type molten material, the substrate is sprayed by the -11 - 201134950 spray method, and the aluminum film can be obtained by rapid cooling and solidification with the compression effect. In the same case, if aluminum is to be used The aluminum film is obtained by spraying the substrate with a material in which indium and a metal selected from the group consisting of titanium, vanadium and a pin are melted in a uniform manner, by rapid cooling solidification and compression effect thereof. The added indium and the metal selected from the group consisting of titanium, vanadium and zirconium are highly dispersed in the aluminum crystal grains by the spraying process, and are kept in direct contact with the aluminum. Since indium (titanium, vanadium, pin) cannot form a stable layer with aluminum. , so the aluminum/indium (titanium, vanadium, cone) interface maintains high energy, and In the ambient atmosphere where moisture exists, it reacts violently with the contact surface with water. In addition, the indium of the added element and the metal from titanium, vanadium and chromium are highly dispersed, and further, due to the expansion of the generated H2 bubble Mechanically, the reaction product mainly composed of AlOOH is not superfied and micronized into the liquid, and the dissolution reaction is continuously and violently carried out at the successively updated reaction interface. The aluminum-indium-such as the above-mentioned is selected from the above. The behavior of the metal systems of titanium, vanadium and zirconium has nothing to do with the purity of aluminum, and is similarly produced in 2N aluminum to 5N aluminum. Also, in the case of aluminum-indium, the impurity copper present in aluminum is present. The content has a great influence on the solubility of the aluminum spray film after the heat history. If the copper content is high (for example, 40 ppm), the solubility of the aluminum spray film after the heat history of the high temperature is poor, and the adhesive film is attached. At the time of film removal treatment, it is difficult to remove the film even if the temperature of the water is raised. Further, when the copper content is low (for example, 1 Oppm), it is necessary to increase the temperature of the water for removing the film from the attached film (for example, 100). Above °C). However, Since aluminum-indium is added with a metal selected from the group consisting of titanium, vanadium and chromium in the amount of -12-201134950, it can exhibit the desired solubility without any relationship with the copper content. Hereinafter, the main description is 4N aluminum-indium-titanium. An example of a water-reactive aluminum composite material formed by using an aluminum-indium-titanium composite material in which indium and titanium are dispersed in 4N aluminum in the same manner as in titanium, and forming a film in a predetermined ambient atmosphere by a spray method. The surface of the substrate to be treated is manufactured by the same. The obtained aluminum-indium-titanium powder film contains crystal grains of indium and titanium in a uniform and highly dispersed state in the aluminum crystal grains (particle size 1 Onm) The aluminum melt film is produced, for example, in the following manner: 4N aluminum, indium, and titanium are prepared, and aluminum is added in an amount of 2.0 to 5.0% by weight of indium, and 0.05 to 1.0% by weight (preferably 0 · 1). ???1.0% by weight, more preferably 0.13~0.6 wt% of titanium, so that indium and titanium are uniformly melted in aluminum, and processed into a rod shape or a line shape as a spray material, for example, by a spray method , in the air, sprayed on a film-forming device to prevent adhesion of the film, etc., under well-known spray conditions. The surface of the member constituting the substrate, and allowed to cool rapidly and coating, whereby a substrate made of a film comprising a desired spray water can be prepared by the reaction of aluminum. The aluminum melt film thus obtained, as described above, is a film in which indium and titanium are present in a highly dispersed state in the aluminum crystal grains. When the substrate coated with the aluminum spray film as described above is immersed in warm water or water vapor is blown, for example, when immersed in warm water of a predetermined temperature, the reaction starts to start to generate hydrogen gas after the start of the immersion and if the reaction continues In the case of indium, etc., the water is blackened by the precipitation of indium or the like, and finally, the molten film is micronized by the intense reaction with water, and all of the particles are dissolved in the warm water, such as aluminum, indium, titanium (vanadium, zirconium), and the like. In this reaction, the higher the water temperature, the more intense the reaction. -13- 201134950 The above-mentioned spray film is described by an example in which a rod-shaped or wire-shaped material is formed by flame spraying, and a flame spray using a powdery material is also possible, and an arc spray or a plasma spray is used. Can also be applied. According to the present invention, the raw material is melted and blown onto the surface of the substrate to be rapidly cooled and solidified in accordance with the above-described melting method to form a molten film. As described above, the constituent members for the film forming chamber such as the adhesion preventing plate or the mask provided in the film forming chamber of the film forming apparatus are formed by using the water-reactive aluminum film of the present invention. After the film processing, the constituent members for the film forming chamber in which the film forming material is inevitably attached can be easily removed, and the deposited film can be easily removed by removing the film. In this case, the treatment liquid is removed, and water, water vapor, or an aqueous solution such as pure water is simply used, and it is possible to prevent damage to the constituent members of the film forming chamber such as the adhesive sheet due to dissolution. The number of such reuses has increased significantly compared to the case of using drugs. In addition, since no drugs are used, the processing cost can be greatly reduced and environmental protection can be achieved. In addition, since most of the film-forming material adhering to the constituent members for the film forming chamber such as the adhesion preventing sheet is not dissolved in water, it is possible to directly recover the solid of the same type as the film forming material. Furthermore, not only does the recycling cost drop dramatically, but the recycling step is also simplified, so that the range of recyclable materials is increased. For example, when the film forming material is a high-priced metal such as a precious metal or a rare metal, if the molten film composed of the water-reactive aluminum composite material of the present invention is used for a film forming chamber constituent member such as an adhesion preventing plate, The film forming chamber having a film which is inevitably adhered in the film formation is immersed in water or water vapor by the constituent member, and the film-attachment material 14 - 201134950 can be removed, so that the precious metal can be contaminated without causing contamination. Or rare metal recycling. The recycling cost is low, and the film forming material can be recovered with high quality. Hereinafter, the present invention will be described in detail based on reference examples and examples. (Reference Example) Using 2N aluminum, 3N aluminum, and 4N aluminum, the relationship between the purity of aluminum in the indium-added aluminum-indium composition, the amount of copper in the aluminum, and the solubility of the obtained melt film was examined. The amount of indium added is based on the weight basis. (a) 2N aluminum (impurity copper: < 400 ppm) - 3.0 wt% indium (b) 3N aluminum (impurity copper: 7 〇 PPm) - 3.0 wt% indium (c) 3N aluminum (impurity copper: below detection limit) 3. Owt% indium (d) 4N aluminum (impurity copper: below detection limit) - 3.0 wt% indium in the above ratio with aluminum and indium 'used in aluminum to uniformly melt indium and processed into a rod shape of the molten material' A molten rod type flame spray (heat source: C2H2-〇2 gas, about 3000 ° C) was blown on the surface of an aluminum substrate to form a spray film. For each of the thus obtained spray films, a heat treatment (atmospheric, 1 hour, furnace cooling) at a normal temperature of ～350 °C was applied to replace the heat history in the film forming process. Immersion of the sprayed film substrate in the state before the heat treatment (normal temperature) and the sprayed film substrate after heat treatment (after the heat history) in 300 ml of pure water at 8 ° C The current density of the liquid (mA/cm2) was used to investigate the solubility of each of the spray films. Discussion on the solubility of 2N aluminum to 4N aluminum aluminum spray film' found that the solubility of 4N aluminum impurity copper is below the detection limit, which is higher than that of 2N and 3N aluminum. Aluminium and 4N aluminum impurities -15-201134950 When the amount is below the detection limit, the heat treatment temperature of 350 °C is 50 mA/cm2 or more, which is soluble. However, when the content of the impurity copper of 2N aluminum and 3N aluminum is 70 ppm or more, the molten film of heat treatment (heat history) of 350 t does not have sufficient solubility. In this case, even if the temperature of the treatment liquid is raised to 100 ° C or more, it cannot be dissolved. Further, for 4N aluminum (impurity copper: 30 ppm) - 2.5 wt% indium and 4 N aluminum (impurity copper: 10 ppm) - 4.0 wt% indium, the same results as described above, heat treatment at 350 ° C (heat history) The molten film is also not sufficiently soluble. [Example 1] In the present embodiment, as follows, aluminum-indium added with 4N aluminum indium, aluminum-indium-titanium in which 4N aluminum is added with indium and titanium, and aluminum-indium added with indium in 5N aluminum are discussed. The relationship between the purity of aluminum in the aluminum-indium composition of titanium and the solubility of the spray film due to the presence or absence of titanium addition (see Fig. 1). The amount of indium and titanium added is based on the weight of aluminum. (a) 4N aluminum (impurity copper: below detection limit) _ 3.0 wt% indium - 0 _ 2 wt % titanium (b) 5N aluminum (impurity copper: below detection limit) - 3.0 wt% indium (c) 4N aluminum (impurity Copper: below the detection limit) -3.0wt% indium, as follows, used in 4N aluminum containing impurities such as iron, antimony, copper, nickel, and carbon, indium-added with indium' to investigate the solubility of impurities in the melt film The impact (see Figure 2). The addition amount of indium and antimony is the basis of the aluminum weight. (a) 4N Ming (impurity copper · l〇PPm, iron: 80ppm, sand: -16- 201134950 1 OOppm 'nickel: <10ppm) - 3.0wt% indium (b) ULMAT 4N Ming (impurity copper: 40ppm, Iron: 40 ppm, sand: 80 ppm, nickel: < lOppm) - 3.5 wt ° / 〇 indium (c) 4N Ming (impurity copper: lOppm, iron: 60 ppm, sand: 100 ppm, nickel: below detection limit) - 3.0 wt % indium (d) ULMAT produces 4N aluminum (impurity copper: 40ppm, iron: llOppm, shixi: lOOppm, nickel: < lOppm, carbon: 30ppm) - 3.0wt% indium (e) China's 3N aluminum (impurity copper: 70ppm, iron: 120ppm, sand · lOOppm, nickel: 30ppm) - 3.0wt% indium, such as the following, used in 4N aluminum with indium aluminum-indium, and 4N aluminum with indium and titanium aluminum-indium-titanium The relationship between the content of the impurity copper in the aluminum in the aluminum-indium composition of titanium added and the solubility of the spray film due to the presence or absence of the addition of titanium (see Fig. 3). The addition amount of indium and titanium is the aluminum weight standard. (a) 4 N aluminum (impurity copper: below detection limit) - 2.7 wt % indium - 0 · 2 0 wt % more than (b) 4N aluminum (impurity copper: 30 ppm) ~ 3. 〇 wt% indium - 0.40 wt% Titanium (c) 4N aluminum (impurity copper: 40 ppm) *~3.〇wt% indium-0.56wt% Titanium (d) 4 N aluminum (impurity copper: below detection limit) _ 3.0 wt % indium (e) 4N aluminum ( Impurity copper: 30ppm) ~3.5wt% indium (f) 4N aluminum (impurity copper · · 40ppm) ~3. 〇wt% indium
再者，如以下’使用於2N鋁添加銦之鋁-銦、於2N -17- 201134950 鋁添加銦及鈦之鋁一銦一鈦、於3 N鋁添加銦之鋁一銦、於 3 N銘添加銦及鈦之銘-銦一欽、於4 N銘添加銦之銘一銦 、及於4N鋁添加銦及鈦之鋁-銦-鈦，探討添加有鈦之鋁 -銦組成中之鋁純度、與鈦添加之有無所致之熔射膜溶解 性之關係（參照圖4 )。銦及鈦之添加量係鋁重量基準。 (a) 2N鋁（雜質銅：檢測界限以下）一 3.0wt%銦 (b ) 2N鋁（雜質銅：檢測界限以下）一 3.0wt%銦一 0,1 5 w t % 鈦 (c) 3N鋁（雜質銅：檢測界限以下）一 3.0wt%銦 (d ) 3N鋁（雜質銅：檢測界限以下）-3.0wt%銦一 0.1 1 w t % it (e) 4N鋁（雜質銅：檢測界限以下）一 3.0wt%銦 (f ) 4N鋁（雜質銅：檢測界限以下）一 3.0wt%銦一 0 · 1 3 w t % 欽 以上述比例配合鋁、銦、鈦，使用於鋁中均勻地熔解 有銦、銦/鈦並加工成棒形狀之熔射材料，以熔棒式火焰 噴射（熱源：C2H2— 02氣體’約3〇00°C)，於大氣環境氣 氛中，吹付於鋁製基材之表面而形成熔射膜。對於如此製 得之各熔射膜，施以常溫〜3 50°c之熱處理（大氣中、1小 時、爐冷）取代成膜製程中所受到之熱歷程。將受熱處理 前之狀態（常溫）之附熔射膜基材、及經熱處理後（經熱 歷程後）之附熔射膜基材浸漬於80 °C之純水300ml中，測 定浸漬液之電流密度以探討各熔射膜溶解性。將所得之結 果示於圖1〜圖4。圖1，係顯示鋁純度、及Ti添加之有無 -18- 201134950 與熔射膜溶解性之關係之圖，圖2，係顯示鋁中之雜質銅 對熔射膜溶解性所造成之影響之圖，圖3，係顯示鋁中之 雜質銅之含量、及Ti添加之有無與熔射膜溶解性之關係之 圖，圖4，係顯示鋁純度、及Ti添加之有無與熔射膜溶解 性之關係之圖。於圖1〜4中，橫軸爲熱處理（熱歷程）溫 度（°C )，縱軸爲溶解電流密度（mA/ cm2 )。 由圖1可知，藉由於4N鋁-銦添加鈦，展現較未添加 鈦之5N鋁-銦更高之熔射膜溶解性。 由圖2可知，熔射膜溶解性大致上不依存於鐵、矽濃 度，但銅使鋁-銦熔射膜之水反應性降低、而使溶解性降 低。 由圖3可知，藉由鈦的添加，展現較未添加鈦較高之 熔射膜溶解性，並且，若於鋁中含有既定量之雜質銅，雖 於鋁-銦組成時之熔射膜溶解性爲低，但藉由鈦的添加， 可展現高熔射膜溶解性。亦即，藉由添加鈦，可減少銅的 影響。於2N鋁及3N鋁的情況下亦顯示相同的傾向。 由圖4可知，藉由分別於2N鋁一銦、3N鋁一銦及4N鋁 -銦添加鈦，較未添加鈦時，展現高溫下之高熔射膜溶解 性。 如上述，藉由鈦的添加展現較高熔射膜溶解性的理由 ’如圖5 ( a )〜（c )所示’係因鈦具有提昇鋁之再結晶 溫度（1 5 0〜2 0 0 °C )的效果之故’若再結晶溫度提高，則 推測結果能抑制姻之偏析、銘—銅。圖5 ( a )及（b )， 係顯示添加元素（質量％ )對8 %冷加工後之4N鋁之再結晶 -19- 201134950 所造成之效果之圖’ （a )係顯示普通添加元素之情形之 以各溫度退火3 0分鐘後之以顯微鏡所測定之再結晶溫度（ °C )之圖，（b)係顯不特殊添加兀素之再結晶溫度（C )之圖，（c)係顯示微量合金元素（質量％)對純銅之再 結晶溫度（200〜250 °C)上昇所造成之影響之圖。由圖5 (a)〜（c)可知，除欽以外，III及銷等亦可使鋁之再結 晶溫度上昇。 〔實施例2〕 於本實施例，如以下’使用對含有既定量之雜質銅之 鋁添加銦之鋁一銦、添加鈦之鋁一銦-鈦、及添加釩之 鋁一銦一釩，探討添加鈦或釩之鋁-銦組成中之鋁中雜質 銅之含量、及鈦或釩添加之有無與熔射膜溶解性之關係（ 參照圖6 )。銦、鈦、釩之添加量，係鋁重量基準。 (a) 4N 銘（雜質銅：40ppm) — 3.0wt% 銦 (b) 4N 銘（雜質銅：40ppm) — 3.0wt% 銦—0.05wt% 釩 (c) 4N 銘（雜質銅：40ppm) —3.0wt% 銦一 0.17wt% 鈦 將鋁、銦、鈦、釩以上述比例配合，使用於鋁中均勻 地熔解有銦及鈦、或銦及釩並加工成棒形狀之熔射材料， 以熔棒式火焰噴射（熱源：C2H2- 02氣體，約3 000°C )， 於大氣環境氣氛中，吹付於鋁製基材之表面而形成熔射膜 。對於如此製得之各熔射膜，施以常溫〜3 5 (TC之熱處理 -20- 201134950 (大氣中、1小時、爐冷）取代成膜製程中所受到之熱歷 程。將受熱處理前之狀態（常溫）之附熔射膜基材、及經 熱處理後（經熱歷程後）之附熔射膜基材浸漬於8 0 °c之純 水3 00ml中，測定浸漬液之電流密度以探討各熔射膜溶解 性。將所得之結果示於圖6。圖6中，橫軸爲熱處理（熱歷 程）溫度（°C )，縱軸爲溶解電流密度（mA/ cm2 )。 由圖6可知，藉由於含有既定量之雜質銅之4>^鋁_銦 添加駄或釩，展現較未添加欽、釩之4N銘-銦更闻之溶射 膜溶解性。於2N鋁、3N鋁及5N鋁的情況下亦顯示相同的 傾向。 如上述，藉由鈦或釩的添加展現較高熔射膜溶解性的 理由，如圖5 ( a )〜（c )所示，係因鈦、釩具有提昇鋁 之再結晶溫度的效果之故。因此，如圖5 ( c )所示，锆的 添加，亦有提昇鋁之再結晶溫度的效果，故與鈦及釩的添 加同樣地展現較高熔射膜溶解性。 〔實施例3〕 於本實施例，與實施例1同樣地，製作如以下之4N鋁 -銦組成之熔射膜，探討熱處理（熱歷程）溫度與各熔射 膜溶解性的關係。 (a) 4N鋁（雜質銅：檢測界限以下）_ 3.0wt%銦 (b) 4N 鋁（雜質銅：40ppm) — 3_0wt% 銦 (c ) 4N鋁（雜質銅：檢測界限以下）—3.0wt%銦（ + 0.00 1 Μ之 CuS04 ) -21 - 201134950 其中，關於上述組成（c ) ’係使 基材之浸漬液中添加有〇.〇〇1M之CuS〇4 於該情況下，於浸溃液中含有Cu2+ (鋪 結果示於圖7。圖7中，橫軸爲熱處理（ )，縱軸爲溶解電流密度（mA/ cm2 ) 由圖7可知，於銅存在的情形（上 ))，顯示相同之溶解傾向，較未含銅 成（a ))，於高溫熱處理（熱歷程） 性低。於2 N鋁、3 N鋁及5 N鋁的情況下 〔實施例4〕 於本實施例，係對於依據實施例1 組成之鋁-銦及鋁_銦-鈦之熔射膜， 275 °C之熱處理（熱歷程）溫度，改變 程）時間製得附熔射膜基材，將該附熔 1同樣地，浸漬於既定之浸漬液中’測 度以探討各熔射膜溶解性（圖8 ) ° (a ) 4N鋁（雜質銅：檢測界限以 2 00°C ) (b ) 4N鋁（雜質銅：檢測界限以 2 5 0〇C ) (c ) 4N鋁（雜質銅：檢測界限以 275 °C ) 用於浸漬附熔射膜 者測定電流密度。 1 : 64ppm )。所得 熱歷程）溫度（t 〇 述組成（b )及（c 的情形（較上述組 溫度之熔射膜溶解 亦顯示相同的傾向 所製作之具有以下 以 2 0 0 t：、25 0 〇C、 其之熱處理（熱歷 射膜基材與實施例 定浸漬液之電流密 下）一 3_0wt% 姻（ 下）—3.0wt% 姻（ 下）一 3.0 w t % 銦（ -22- 201134950 (d ) 4N鋁（雜質銅：檢測界限以下）一 2.7wt%錮一 0.20wt%鈦(250〇C ) (e) 4N 鋁（雜質銅：30ppm) ~3.〇wt% 銦—〇.4〇wt% 鈦（25 0°C ) (f) 4N 鋁（雜質銅：40ppm) -3.〇wt% 銦-〇.56wt% 鈦（250°C ) (g ) 4N鋁（雜質銅：檢測界限以下）一 2.7wt%銦一 0.20wt%鈦(2 7 5 °C ) (h) 4N 鋁（雜質銅：30ppm) — 3.〇wt% 銦—〇.4〇wt% 鈦（27 5 〇C ) (i) 4N 鋁（雜質銅：40ppm) -3.0wt% 銦-0.56wt% 鈦（275〇C ) 將所得之結果示於圖8。圖8中，橫軸爲熱處理（熱歷 程）時間（hr )，縱軸爲溶解電流密度（mA/ cm2 )。由 圖8可知，於1 〇〜2〇小時之熱處理（熱歷程）時間下，熔 射膜溶解性大致一定而安定化。因此，推斷熔射膜溶解性 可以20小時之熱處理（熱歷程）時間來判定。 又，若比較圖8中之熱處理（熱歷程）溫度2 5 之情 形之熔射膜（上述組成（b ) 、 ( d ) 、（ e )及（f))之 溶解性，則可知添加既定量鈦所成之熔射膜，顯示較未添 加鈦之熔射膜高出約2倍之溶解性。熱處理（熱歷程）溫 度275 t：之情形下亦與2 5 0°C時顯示大致同高之溶解性。 再者，可知藉由添加鈦，可緩和雜質銅對熱處理（熱 歷程）的影響。 -23- 201134950 〔實施例5〕 於本實施例’係對於依據實施例丨所製作之具有以下 組成之鋁-銦及鋁-銦-鈦之熔射膜，以2 5 0 t之熱處理 (熱歷程）溫度，延長其之熱處理（熱歷程）時間至100 小時製得附熔射膜基材，將該附熔射膜基材與實施例1同 樣地，浸漬於既定之浸漬液中，測定浸漬液之電流密度以 探討各熔射膜溶解性（圖9 )。 (a) 4N 銘（雜質銅：40ppm) — 3.3wt% 銦—0_17wt% 鈦 (b) 4N 銘（雜質銅：40ppm) — 2.9wt% 銦—0_13wt% 鈦 (c) 4Ν|呂（雜質銅：40ppm) — 3.3wt%銦—0.28wt% 鈦 (d) 5N 銘（雜質銅：40ppm) — 3.0wt% 銦 由圖9可知，藉由添加鈦，即使受到1 0 0小時之長時間 之熱歷程，亦可維持熔射膜溶解性，而若未添加鈦，則熔 射膜溶解性極低’經過2〇小時後幾乎變零。 又，對（a) 4N 鋁（雜質銅：40ppm) — 3.0wt% 銦— 0.17wt%駄、（b) 4N銘（雜質銅：40ppm) — 3.0wt%銦一 0.17wt%欽、及（c) 5N 銘（雜質銅：40ppm) — 3.0wt% 姻 ，以與上述同樣方式’探討受到200小時之熱歷程時，在 2 5 0 °C之熱處理（熱歷程）時間與溶解時間之關係。將其 結果示於圖1 〇 ° 由圖1 0可知，藉由添加鈦，於短時間之溶解時間熔射 •24- 201134950 膜即溶解。 〔實施例6〕 於本實施例，係對（a ) 4N鋁（雜質銅：40PPm )— 3.0wt% 銦、（b ) 4N鋁（雜質銅：40ppm ) - 3.0wt°/〇 銦、 及（c) 4N 鋁（雜質銅：40ppm) — 3.0wt% 銦一0.2wt% 鈦 ，與實施例1同樣地製造熔射膜並以3 〇 〇 °C熱處理1小時後 之溶射膜，觀測其之SEM像，探討銦之析出粒子。組成（ a )〜（c )係分別對應於圖1 1 ( a )〜（c )。圖中’白色 部分即爲所析出之銦粒子。 由圖1 1 ( a )〜（c )可知，銦粒子，係以組成（c ) <組成（a ) <組成（b )依序增大。由此亦可知，若銅存 在則熔射膜溶解性低，而藉由添加鈦可提高熔射膜溶解性 〔實施例7〕 於本實施例’係將依據實施例〗所製作之圖3中所示組 成（c)中之鈦含量之0.56 wt%’取代爲〇_〇3 wt%、0.80 wt% ' 1.0 wt%、及1 ·20 wt% ’探討熔射膜溶解性。其之結 果，鈦含量爲〇·03 wt%時顯示與未添加鈦時大致相同程度 之熔射膜溶解性’ 0·80 wt%及I·0 wt%與0.56 wt%時顯示大 致相同程度之熔射膜溶解性’又’ 1.20 wt%時，膜較1 .〇 wt%時硬、對水的溶解性低。 -25- 201134950 〔實施例8〕 使用設置有以實施例1所得之4N鋁（雜質銅：40ppm )—3.0wt%銦-0.20wt%鈦熔射膜、4N鋁（雜質銅： 40ppm ) - 3.0wt%銦-0.56wt%鈦熔射膜、以及實施例2所 得之4N鋁（雜質銅：40ppm ) - 3.0wt%銦一0.05wt%鈦熔 射膜被覆表面之防止附著板的濺鑛裝置，實施鉑（Pt)成 膜30循環後，將附著有該鉑之防止附著板取出，以80°C之 溫水處理之結果，於30分鐘熔射膜溶解，由防止附著板將 鉑之附著膜除膜。因此，可容易地回收成膜材料之鉑。此 時，於溫水中沉澱有A100H。又，使用以實施例1所製得 之4N鋁（雜質銅：4〇ppm ) — 3.0wt%銦熔射膜被覆表面之 防止附著板同樣地實施的結果，難以由防止附著板將附著 膜除膜。 若以本發明之水反應性鋁複合材料所構成之鋁膜，被 覆濺鍍法、真空蒸鍍法、離子沉積法、CVD法等用以形成 金屬或金屬化合物之薄膜之真空成膜裝置內之成膜室用構 成構件的表面，則可於水分存在之環境氣氛中，將成膜製 程中附著於該成膜室用構成構件之表面之不可避免的附著 膜除膜、回收。因此，本發明，於使用該等成膜裝置之領 域’例如半導體元件或電子相關機器等之技術領域中，可 增加成膜室用構成構件之再利用次數，而能利用於含有價 金屬之成膜材料之回收。 【圖式簡單說明】 -26- 201134950 圖1 ’顯示用以表示實施例1所得之鋁熔射膜中之鋁純 度、或鈦添加之有無對熔射膜溶解性所造成之影響之熱處 理（熱歷程）溫度（°c )與溶解電流密度（mA/ cm2 )之 關係圖。 圖2 ’顯示用以表示實施例1所得之鋁熔射膜中之鋁中 之雜質銅對熔射膜溶解性所造成之影響之熱處理（熱歷程 )溫度（°C )與溶解電流密度（mA/ cm2 )之關係圖。 圖3 ’顯示用以表示實施例1所得之鋁熔射膜中之鋁中 之雜質銅之含量、或鈦添加之有無對熔射膜溶解性所造成 之影響之熱處理（熱歷程）溫度（t )與溶解電流密度（ mA/cm2)之關係圖。 圖4，顯示用以表示實施例1所得之鋁熔射膜中之鋁純 度、或鈦添加之有無對熔射膜溶解性所造成之影響之熱處 理（熱歷程）溫度（°C )與溶解電流密度（mA / cm2 )之 關係圖。 圖5 ( a )及（b )，係顯示添加元素（質量％ )對8 % 冷加工後之4N鋁之再結晶所造成之效果之圖。圖5 ( a )， 係顯示普通添加元素之情形之以各溫度退火3 0分鐘後之以 顯微鏡所測定之再結晶溫度（°C )。圖5 ( b )，係顯示特 殊添加元素之再結晶溫度（°C )。圖5 ( c )，係顯示微量 合金元素（質量％ )對純銅之再結晶溫度（°C )上昇所造 成之影響之圖。 圖6，係顯示用以表示實施例2所得之鋁熔射膜中之添 加有鈦或釩之Al— In組成中之鋁中之雜質銅之含量、或鈦 -27- 201134950 或釩添加之有無對熔射膜溶解性所造成之影響之熱處理（ 熱歷程）溫度（°C )與溶解電流密度（mA / cm2 )之關係 圖。 圖7，係顯示用以表示雜質Cu對實施例3所得之鋁熔射 膜之影響之熱處理（熱歷程）溫度（°C )與溶解電流密度 (mA / cm2)之關係圖。 圖8，係顯示用以表示實施例4所得之鋁熔射膜中之熱 處理（熱歷程）溫度（°C )與熱處理（熱歷程）時間等對 熔射膜溶解性所造成之影響之熱處理（熱歷程）時間（hr )與溶解電流密度（mA/ cm2 )之關係圖。 圖9，係顯示用以表示實施例5所得之鋁熔射膜中之鈦 添加之有無所致之熱處理（熱歷程）時間（hr )與溶解電 流密度（mA / cm2)之關係圖。 圖1 〇，係顯示IT施例5所得之鋁熔射膜受到200小時之 熱歷程時之250 °C之熱處理（熱歷程）時間（hr )與溶解 時間（hr)之關係圖。 圖1 1，係顯示由實施例6所得之附鋁熔射膜基材除膜 後之附著膜（熔射膜）之狀態的S EM像。圖1 1 ( a )，係 4N鋁（雜質銅：檢測界限以下）-3.0wt%銦時所觀測到之 SEM像。圖 1 1 ( b ) ’係 4N鋁（雜質銅：40ppm ) - 3.0wt% 銦時所觀測到之S E Μ像》圖1 1 ( c )，係4 N鋁（雜質銅： 4 0 p p m ) - 3.0 w t %銦-0.2 w t %鈦時所觀測到之S E Μ像。 -28-Furthermore, as follows, 'aluminum-indium used for adding 2N aluminum to indium, aluminum to indium-titanium added with indium and titanium to 2N-17-201134950, and aluminum-indium added with indium to 3N aluminum, at 3 N Adding the indium and titanium inscription - Indium Yiqin, adding indium indium to 4 N, and indium and titanium in aluminum and indium-titanium in 4N aluminum, discussing the purity of aluminum in the aluminum-indium composition with titanium added The relationship between the solubility of the spray film and the presence or absence of the addition of titanium (see Fig. 4). The addition amount of indium and titanium is based on the weight of aluminum. (a) 2N aluminum (impurity copper: below detection limit) - 3.0 wt% indium (b) 2N aluminum (impurity copper: below detection limit) - 3.0 wt% indium - 0, 15 wt % Titanium (c) 3N aluminum ( Impurity copper: below detection limit) 3.0 wt% indium (d) 3N aluminum (impurity copper: below detection limit) - 3.0 wt% indium - 0.1 1 wt % it (e) 4N aluminum (impurity copper: below detection limit) 3.0wt% indium (f) 4N aluminum (impurity copper: below the detection limit) - 3.0wt% indium - 0 · 1 3 wt % The above ratio is combined with aluminum, indium, titanium, used in aluminum to uniformly melt indium, Indium/titanium is processed into a rod-shaped spray material, which is blown onto the surface of an aluminum substrate in a molten atmosphere by a molten rod flame spray (heat source: C2H2-02 gas 'about 30,000 ° C). A spray film is formed. For each of the thus obtained melted films, a heat treatment (atmosphere, 1 hour, furnace cooling) at a normal temperature of ~3 50 °C was applied instead of the heat history in the film forming process. The molten film substrate attached to the state before the heat treatment (normal temperature) and the sprayed film substrate after heat treatment (after the heat history) are immersed in 300 ml of pure water at 80 ° C to measure the current of the immersion liquid. Density to investigate the solubility of each spray film. The results obtained are shown in Figures 1 to 4. Figure 1 is a graph showing the relationship between the purity of aluminum and the presence or absence of Ti, -18-201134950, and the solubility of the spray film. Figure 2 is a graph showing the effect of impurity copper in aluminum on the solubility of the spray film. Figure 3 shows the relationship between the content of copper in the aluminum and the presence or absence of Ti added to the solubility of the spray film. Figure 4 shows the purity of aluminum and the presence or absence of Ti and the solubility of the spray film. Diagram of the relationship. In Figs. 1 to 4, the horizontal axis represents the heat treatment (thermal history) temperature (°C), and the vertical axis represents the dissolved current density (mA/cm2). As can be seen from Fig. 1, the addition of titanium to 4N aluminum-indium exhibits higher melt film solubility than 5N aluminum-indium without added titanium. As is apparent from Fig. 2, the solubility of the molten film is not substantially dependent on the concentrations of iron and antimony. However, copper lowers the water reactivity of the aluminum-indium melt film and lowers the solubility. As can be seen from Fig. 3, the addition of titanium exhibits a higher solubility of the spray film than the unadded titanium, and if the aluminum contains a certain amount of impurity copper, the melt film dissolves in the aluminum-indium composition. The property is low, but the addition of titanium can exhibit high melt film solubility. That is, by adding titanium, the influence of copper can be reduced. The same tendency was also observed in the case of 2N aluminum and 3N aluminum. As can be seen from Fig. 4, the addition of titanium to 2N aluminum-indium, 3N aluminum-indium, and 4N aluminum-indium, respectively, exhibits high melt film solubility at high temperatures when titanium is not added. As described above, the reason for the solubility of the higher melt film by the addition of titanium is as shown in Fig. 5 (a) to (c) because the titanium has a recrystallization temperature of elevated aluminum (1,500 to 20,000). The effect of °C) If the recrystallization temperature is increased, the result is that the segregation of the marriage and the copper can be suppressed. Fig. 5 (a) and (b) show the effect of the added element (% by mass) on the recrystallization of 4N aluminum after 8% cold working-19- 201134950' (a) shows the case of ordinary added elements The graph of the recrystallization temperature (°C) measured by the microscope after annealing for 30 minutes at each temperature, (b) shows the recrystallization temperature (C) of the non-specially added alizarin, and (c) shows A graph showing the effect of trace alloying elements (% by mass) on the rise of pure copper recrystallization temperature (200 to 250 °C). As can be seen from Fig. 5 (a) to (c), in addition to the Qin, III, the pin, and the like can also increase the recrystallization temperature of aluminum. [Embodiment 2] In the present embodiment, as follows, the use of aluminum-indium with indium added to aluminum containing a predetermined amount of impurity copper, aluminum-indium-titanium added with titanium, and aluminum-indium-vanadium added with vanadium are discussed. The content of impurity copper in aluminum in the aluminum-indium composition of titanium or vanadium, and the presence or absence of addition of titanium or vanadium to the solubility of the spray film (see Fig. 6). The addition amount of indium, titanium, and vanadium is based on the weight of aluminum. (a) 4N Ming (Impurity Copper: 40ppm) — 3.0wt% Indium (b) 4N Ming (Impurity Copper: 40ppm) — 3.0wt% Indium—0.05wt% Vanadium (c) 4N Ming (Impurity Copper: 40ppm) —3.0 Wt% Indium-0.17wt% Titanium is alloyed with aluminum, indium, titanium and vanadium in the above ratio. It is used in aluminum to uniformly melt indium and titanium, or indium and vanadium and process into a rod-shaped spray material. A flame spray (heat source: C2H2- 02 gas, about 3 000 ° C) is blown onto the surface of an aluminum substrate to form a spray film in an atmospheric atmosphere. For each of the thus obtained spray films, a heat history of ~30 (TC heat treatment -20-201134950 (atmosphere, 1 hour, furnace cooling) is substituted for the heat history in the film forming process. The molten film substrate attached to the state (normal temperature) and the sprayed film substrate after heat treatment (after the heat history) are immersed in 300 ml of pure water at 300 ° C, and the current density of the immersion liquid is measured to investigate The melting film solubility is shown in Fig. 6. In Fig. 6, the horizontal axis represents the heat treatment (thermal history) temperature (°C), and the vertical axis represents the dissolved current density (mA/cm2). By means of the inclusion of a certain amount of impurity copper 4 > ^ aluminum _ indium added bismuth or vanadium, showing the solvent solubility of 4N Ming-Indium which is not added with Qin and vanadium. In 2N aluminum, 3N aluminum and 5N aluminum In the case of the same, the same tendency is also exhibited. As described above, the reason why the solubility of the higher melt film is exhibited by the addition of titanium or vanadium is as shown in Fig. 5 (a) to (c), because the titanium and vanadium are promoted. The effect of the recrystallization temperature of aluminum. Therefore, as shown in Fig. 5 (c), the addition of zirconium also enhances the recrystallization of aluminum. In the same manner as in the case of addition of titanium and vanadium, the solubility of the molten film is higher. [Example 3] In the present example, in the same manner as in Example 1, a 4N aluminum-indium composition was melted as follows. Film, to investigate the relationship between heat treatment (thermal history) temperature and solubility of each spray film. (a) 4N aluminum (impurity copper: below detection limit) _ 3.0wt% indium (b) 4N aluminum (impurity copper: 40ppm) — 3_0wt% indium (c) 4N aluminum (impurity copper: below the detection limit) - 3.0 wt% indium (+ 0.00 1 Μ CuS04) -21 - 201134950 wherein, in the above composition (c) 'the substrate is impregnated CuS〇4 with 〇.〇〇1M was added. In this case, Cu2+ was contained in the immersion liquid (the results are shown in Fig. 7. In Fig. 7, the horizontal axis is heat treatment ( ), and the vertical axis is dissolved current density (mA). / cm2) It can be seen from Fig. 7 that in the case where copper is present (top), the same tendency to dissolve is exhibited, and (a) is not contained in copper, and the heat treatment (thermal history) is low. In the case of 2 N aluminum, 3 N aluminum, and 5 N aluminum [Example 4] In this example, for a spray film of aluminum-indium and aluminum_indium-titanium according to Example 1, 275 ° C Heat treatment (heat history) temperature, change process) time to obtain a spray film substrate, the same as the immersion in a predetermined immersion liquid 'measurement to explore the solubility of each spray film (Figure 8) ° (a) 4N aluminum (impurity copper: detection limit at 200 ° C) (b) 4N aluminum (impurity copper: detection limit at 2 50 ° C) (c) 4N aluminum (impurity copper: detection limit at 275 ° C) For the impregnation of the spray film, the current density is determined. 1 : 64ppm ). The obtained heat history) temperature (t 〇 组成 组成 ( 组成 组成 组成 组成 组成 组成 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The heat treatment (the thermal history film substrate is intimate with the current of the impregnating solution of the embodiment) is 3-0 wt% (in) - 3.0 wt% (in) a 3.0 wt % indium ( -22-201134950 (d) 4N Aluminum (impurity copper: below the detection limit) - 2.7 wt% 锢 a 0.20 wt% titanium (250 〇 C) (e) 4N aluminum (impurity copper: 30 ppm) ~ 3. 〇 wt% indium - 〇. 4 〇 wt% titanium (25 0 ° C ) (f) 4N aluminum (impurity copper: 40ppm) -3. 〇wt% indium-〇.56wt% titanium (250 ° C) (g) 4N aluminum (impurity copper: below the detection limit) -2.7 Wt% indium-0.20wt% titanium (2 7 5 °C) (h) 4N aluminum (impurity copper: 30ppm) — 3.〇wt% indium—〇.4〇wt% titanium (27 5 〇C ) (i) 4N aluminum (impurity copper: 40 ppm) - 3.0 wt% indium - 0.56 wt% titanium (275 〇 C) The results obtained are shown in Fig. 8. In Fig. 8, the horizontal axis is the heat treatment (thermal history) time (hr), vertical The axis is the dissolved current density (mA/cm2). It can be seen from Fig. 8 that the heat treatment is performed at 1 〇 2 hours. (Heat history) time, the solubility of the spray film is approximately constant and stabilized. Therefore, it is estimated that the solubility of the spray film can be determined by the heat treatment (thermal history) time of 20 hours. Also, if the heat treatment (heat) in Fig. 8 is compared In the case of the solubility of the above-mentioned composition (b), (d), (e), and (f) in the case of a temperature of 2 5, it is known that a molten film formed by adding a predetermined amount of titanium is displayed. The addition of the titanium spray film is about twice as high as the solubility. The heat treatment (heat history) temperature of 275 t: also shows the solubility at about the same height as at 250 ° C. Furthermore, it can be seen that by adding Titanium can alleviate the influence of the impurity copper on the heat treatment (thermal history). -23- 201134950 [Example 5] In the present example, the aluminum-indium and aluminum-indium having the following composition prepared according to the examples were used. The molten film of titanium is heat-treated (thermal history) temperature of 250 k, and the heat treatment (heat history) time is extended to 100 hours to obtain a film substrate, and the film substrate is implemented. Example 1 was similarly immersed in a predetermined immersion liquid to measure the current of the immersion liquid. Density to investigate the solubility of each spray film (Fig. 9). (a) 4N Ming (impurity copper: 40ppm) - 3.3wt% indium - 0_17wt% Titanium (b) 4N Ming (impurity copper: 40ppm) - 2.9wt% indium —0_13wt% Titanium (c) 4Ν|Lu (impurity copper: 40ppm) — 3.3wt% indium—0.28wt% Titanium (d) 5N Ming (impurity copper: 40ppm) — 3.0wt% Indium can be seen from Figure 9 by adding Titanium maintains the solubility of the spray film even if it is subjected to a heat history of 100 hours. If titanium is not added, the solubility of the spray film is extremely low, and it becomes almost zero after 2 hours. Further, for (a) 4N aluminum (impurity copper: 40 ppm) - 3.0 wt% indium - 0.17 wt% 駄, (b) 4N 铭 (impurity copper: 40 ppm) - 3.0 wt% indium - 0.17 wt%, and (c 5N Ming (Impurity Copper: 40ppm) - 3.0wt% In the same way as above, the relationship between heat treatment (thermal history) time and dissolution time at 250 °C is investigated. The results are shown in Fig. 1. 〇 ° It can be seen from Fig. 10 that by adding titanium, it is sprayed in a short time of dissolution time. • 24-201134950 The film dissolves. [Example 6] In the present example, (a) 4N aluminum (impurity copper: 40 ppm) - 3.0 wt% indium, (b) 4N aluminum (impurity copper: 40 ppm) - 3.0 wt / 〇 indium, and ( c) 4N aluminum (impurity copper: 40 ppm) - 3.0 wt% indium - 0.2 wt% titanium, a spray film was produced in the same manner as in Example 1 and heat-treated at 3 ° C for 1 hour, and the SEM was observed. Like, to explore the precipitation of indium particles. Compositions (a) to (c) correspond to Figs. 1 1 (a) to (c), respectively. The white portion in the figure is the precipitated indium particles. 1 (a) to (c), the indium particles are sequentially increased in composition (c) < composition (a) < composition (b). Therefore, it is also known that if the presence of copper is low, the solubility of the melted film is low, and the solubility of the sprayed film can be improved by adding titanium [Example 7] In the present embodiment, it will be produced in Fig. 3 according to the embodiment. The 0.56 wt% of the titanium content in the composition (c) shown was replaced by 〇_〇3 wt%, 0.80 wt% '1.0 wt%, and 1 ·20 wt%' to investigate the melt film solubility. As a result, when the titanium content is 〇·03 wt%, the melt film solubility of approximately 0. 80 wt% and I·0 wt% and 0.56 wt% are approximately the same as those when titanium is not added. When the solubility of the spray film is '1', the film is harder than 1.wt%, and has low solubility in water. -25-201134950 [Example 8] Using 4N aluminum (impurity copper: 40 ppm) obtained in Example 1 - 3.0 wt% indium - 0.20 wt% titanium spray film, 4N aluminum (impurity copper: 40 ppm) - 3.0 Wt% indium-0.56 wt% titanium spray film, and 4N aluminum (impurity copper: 40 ppm) obtained in Example 2 - 3.0 wt% indium-0.05 wt% titanium spray film coating surface of the splash plate preventing adhesion plate, After platinum (Pt) film formation was carried out for 30 cycles, the platinum-preventing adhesion plate was taken out, and as a result of treatment with warm water of 80 ° C, the spray film was dissolved in 30 minutes, and the adhesion film of the platinum was prevented by the adhesion plate. Remove the membrane. Therefore, the platinum of the film-forming material can be easily recovered. At this time, A100H was precipitated in warm water. Further, as a result of the same effect of the adhesion preventing plate coated with the 4N aluminum (impurity copper: 4 〇 ppm) - 3.0 wt% indium spray film obtained in Example 1, it was difficult to remove the adhering film by the adhesion preventing plate. membrane. The aluminum film formed of the water-reactive aluminum composite material of the present invention is coated in a vacuum film forming apparatus for forming a film of a metal or a metal compound by a sputtering method, a vacuum deposition method, an ion deposition method, a CVD method, or the like. In the surface of the constituent member for the film forming chamber, the unavoidable adhesion film adhering to the surface of the constituent member for the film forming chamber in the film forming process can be removed and recovered in the atmosphere in which the film is formed. Therefore, the present invention can increase the number of reuses of constituent members for a film forming chamber in the field of using such a film forming apparatus, such as a semiconductor element or an electronic related machine, and can be utilized for the formation of a valence metal. Recovery of membrane materials. BRIEF DESCRIPTION OF THE DRAWINGS -26- 201134950 FIG. 1 ' shows a heat treatment (heat) for indicating the influence of the purity of aluminum in the aluminum spray film obtained in Example 1, or the presence or absence of titanium addition on the solubility of the spray film. History) The relationship between temperature (°c) and dissolved current density (mA/cm2). Figure 2' shows the heat treatment (thermal history) temperature (°C) and the dissolved current density (mA) for indicating the influence of the impurity copper in the aluminum in the aluminum spray film obtained in Example 1 on the solubility of the spray film. / cm2 ) diagram. Fig. 3' shows the heat treatment (thermal history) temperature for indicating the influence of the content of the impurity copper in the aluminum in the aluminum spray film obtained in Example 1, or the presence or absence of the addition of titanium on the solubility of the spray film. ) vs. dissolved current density (mA/cm2). Figure 4 is a graph showing the heat treatment (thermal history) temperature (°C) and the dissolution current for indicating the influence of the purity of aluminum in the aluminum spray film obtained in Example 1 or the presence or absence of titanium addition on the solubility of the spray film. A plot of density (mA / cm2). Fig. 5 (a) and (b) show the effect of the added element (% by mass) on the recrystallization of 4% aluminum after 8% cold working. Fig. 5 (a) shows the recrystallization temperature (°C) measured by a microscope after annealing for 30 minutes at each temperature in the case of a conventional additive element. Figure 5 (b) shows the recrystallization temperature (°C) of the special added element. Fig. 5 (c) shows the effect of a trace amount of alloying elements (% by mass) on the rise of the recrystallization temperature (°C) of pure copper. Figure 6 is a graph showing the content of impurity copper in aluminum in the Al-In composition to which titanium or vanadium is added in the aluminum spray film obtained in Example 2, or the presence or absence of titanium 27-201134950 or vanadium addition. A graph showing the relationship between the heat treatment (thermal history) temperature (°C) and the dissolved current density (mA / cm2) of the influence of the solubility of the spray film. Fig. 7 is a graph showing the relationship between the heat treatment (heat history) temperature (°C) and the dissolved current density (mA / cm2) for indicating the influence of the impurity Cu on the aluminum spray film obtained in Example 3. Fig. 8 is a view showing the heat treatment for the influence of the heat treatment (thermal history) temperature (°C) and the heat treatment (heat history) time in the aluminum melt film obtained in Example 4 on the solubility of the spray film ( Thermal history) Time (hr) versus dissolved current density (mA/cm2). Fig. 9 is a graph showing the relationship between the heat treatment (thermal history) time (hr) and the dissolved current density (mA / cm2) for indicating the presence or absence of the addition of titanium in the aluminum spray film obtained in Example 5. Fig. 1 is a graph showing the relationship between the heat treatment (heat history) time (hr) and the dissolution time (hr) at 250 °C in the thermal history of the aluminum spray film obtained in IT Example 5. Fig. 1 is a view showing the S EM image of the state of the adhering film (fusion film) after the film was removed from the aluminum-attached film substrate obtained in Example 6. Fig. 1 1 (a) is an SEM image observed when 4N aluminum (impurity copper: below the detection limit) - 3.0 wt% indium. Figure 1 1 (b) 'SE 4N aluminum (impurity copper: 40ppm) - 3.0wt% indium observed in the SE image" Figure 1 1 (c), is 4 N aluminum (impurity copper: 40 ppm) - The SE artifact observed when 3.0 wt % indium - 0.2 wt % titanium. -28-