1223354 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明） I：發明所屬之技術領域3 本案為審查中之申請案第10/161，192號，申請日2002 年5月28曰之連續部分。 5 發明領域 概略言之，本發明係有關一種用於製造半導體加工設備 之結合金。特別本發明係有關一種包含潔淨鋁合金之結構， 該結構當用於製造半導體加工室組成元件時特別有利。 【先前技術】 10 發明背景 半導體加工處理設計多種不同的化學及物理處理，因 而於基板上形成微縮積體電路。組成該積體電路之材料層 例如係經由化學氣相沉積、物理氣相沉積及磊晶生長形成 。部分材料層使用光阻罩以及乾蝕刻及濕蝕刻技術圖案化 15 。經由將攙雜劑植入特定位置而於層内部形成圖案。形成 積體電路之基板可為矽、砷化鎵、玻璃或任何其它適當材 料。 多種用於製造積體電路之半導體方法係採用鹵素或含 鹵素之氣體或電漿。若干加工處理使用含齒素液體。此外 因用來化成積體電路之處理留下污染物沉積於處理裝置表 面上，此種沉積物常見使用電漿清潔技術去除，該電聚清 W技術“用至少―種含函素氣體。清潔程序包含使用去離 子水濕擦拭，接著使用異丙醇擦拭。 賴泛用作為半導體製造設餘的組成漏，偶爾由於 6 1223354 玖、發明說明 紹具有傳導性質，但通常係由於鋁容易製造且可以合理價 格取得。但鋁易與鹵素（如氯、氟及反應而產生例如 A1C13(或 Al2ci6);或 A1F3 ;或 AlBr3(或 Al2Br6)。鋁-氟化合 物可能由處理裝置元件表面片落，造成元件本身的溶蝕， 5以及成為處理室（以及於處理室内製造的元件）之微粒污染 源。大部分含鋁及氯之化合物以及多種含鋁及溴之化合物 ’於半導體加工條件下為氣態，且離開鋁結構，形成空隙 ’空隙造成結構不穩定，而產生完整性有疑問的表面。 保護加工裝置内部之鋁表面之較佳手段為陽極化塗覆 10 。陽極化典型為電解氧化處理，電解氧化處理於鋁表面上 形成完整氧化鋁塗層。儘管使用陽極化保護層，半導體加 工裝置的陽極化鋁元件例如CVD反應器室内之感受器以及 蝕刻處理室内之氣體分配板等元件壽命，因保護性陽極化 膜之漸進分解而受限制。保護性陽極化膜故障，結果導致 1 5反應為至内之過度微粒生成，需要停機維修，更換故障的 I呂元件，以及由處理室内其餘部分清除微粒。1223354 发明 Description of the invention (The description of the invention should state: the technical field, prior art, content, implementation, and drawings of the invention briefly) I: the technical field to which the invention belongs 3 This case is the application under review No. 10/161 , No. 192, the continuation of the application date May 28, 2002. 5 Field of the Invention In brief, the present invention relates to a bonding metal used for manufacturing semiconductor processing equipment. In particular, the present invention relates to a structure including a clean aluminum alloy, which is particularly advantageous when used for manufacturing a semiconductor processing chamber component. [Prior Art] 10 Background of the Invention Semiconductor processing processes design a variety of different chemical and physical processes, thereby forming micro-condensed body circuits on the substrate. The material layers constituting the integrated circuit are formed by, for example, chemical vapor deposition, physical vapor deposition, and epitaxial growth. Part of the material layer is patterned using photoresist masks and dry and wet etching techniques 15. A pattern is formed inside the layer by implanting the dopant at a specific location. The substrate on which the integrated circuit is formed may be silicon, gallium arsenide, glass, or any other suitable material. Many semiconductor methods for manufacturing integrated circuits use halogens or halogen-containing gases or plasmas. Several processing uses tooth-containing liquids. In addition, due to the processing used to form integrated circuits, pollutants are deposited on the surface of the processing device. Such deposits are commonly removed using plasma cleaning technology, which uses "at least a kind of gas containing selenium. Cleaning The procedure includes wet wiping with deionized water, followed by wiping with isopropyl alcohol. Lai Fan is used as a component of semiconductor manufacturing equipment. Occasionally, it is conductive due to 6 1223354 发明, invention description, but usually because aluminum is easy to manufacture and can Obtained at a reasonable price. However, aluminum is easy to react with halogens (such as chlorine, fluorine, and react to produce, for example, A1C13 (or Al2ci6); or A1F3; or AlBr3 (or Al2Br6). Aluminum-fluorine compounds may fall off the surface of the processing device components, causing the components Its own dissolution, 5 and become a source of particulate pollution in the processing chamber (and components manufactured in the processing chamber). Most of the compounds containing aluminum and chlorine and various compounds containing aluminum and bromine 'are gaseous under semiconductor processing conditions, and leave aluminum Structures that form voids' voids cause structural instability and create a surface with questionable integrity. Protect aluminum inside the processing unit The preferred method is anodizing coating 10. Anodizing is typically electrolytic oxidation treatment, which forms a complete alumina coating on the aluminum surface. Although anodized protective layers are used, anodized aluminum components of semiconductor processing equipment such as The life of components such as susceptors in CVD reactors and gas distribution plates in etching chambers is limited due to the gradual decomposition of the protective anodized film. The protective anodized film malfunctions, resulting in excessive 15-micron particle generation. Need to shut down for maintenance, replace the faulty I Lu element, and remove particles from the rest of the processing room.
Miyashita等人於美國專利第5,039,388號，核發曰期 1991年8月13日，說明一種成對用於半導體處理室之電漿、生 成電極。電極係由高純度鋁或鋁合金製成，電極表面上^帶 20有鉻酸陽極膜。鉻酸陽極化表面據稱於含氟氣體存在下， 用於電漿處理方法時，可大為改善耐用性。電極被描述為 由高純度鋁例如 JIS 1050、1100、3003、5052、5053 及 \61 或類似的合金例如含2至6%重量比鎂之銀_鎂合金製成。Miyashita et al., U.S. Patent No. 5,039,388, issued August 13, 1991, describe a pair of plasma and electrode formation for use in a semiconductor processing chamber. The electrode system is made of high-purity aluminum or aluminum alloy, and the surface of the electrode is provided with a chromic anode film. Chromic acid anodized surfaces are said to greatly improve durability when used in a plasma treatment method in the presence of a fluorine-containing gas. The electrode is described as being made of high-purity aluminum such as JIS 1050, 1100, 3003, 5052, 5053, and \ 61 or similar alloys such as a silver-magnesium alloy containing 2 to 6% magnesium by weight.
Berc謂等人之美國專利第5,756,222號，核發日期^% 7 1223354 玖、發明說明 年5月26日，名稱「半導體處理設備用之防蝕性鋁物件」， 况明一種可用於半導體加工處理之製造物件，該製造物件 包含一本體其係由雙含量約〇1%至約15%重量比之高純度 秀—感哈金製成，於全體物件或至少於表面區等欲形成為 防姓ϋ以及雜貝原子含量低於〇·2<)/❹重量比。特別值得一 提之雜質原子包括贫、鐵、鋼、絡及铸。高純度紹·鎮合 金可由内聚薄膜覆蓋，該内聚薄膜具有^寒透性，但實質 上不可通過此種薄膜例如包括氧化鋁或氮化鋁。(本專 避寒鸦示之主題全文以弓丨用方式併入此處。 ..A'·-... 10Berc refers to U.S. Patent No. 5,756,222, et al., Issued date ^% 7 1223354 玖, invention description May 26, the name "corrosion-resistant aluminum objects for semiconductor processing equipment", a kind of manufacturing that can be used for semiconductor processing An article, the article of manufacture comprises a body made of a high-purity show-gangan, which has a double content of about 0.01% to about 15% by weight, and is to be formed as an anti-surname in the entire article or at least on the surface area, and The heteroshell atom content is lower than 0.2 <) / ❹ by weight. Particularly noteworthy impurity atoms include lean, iron, steel, alloy and cast. The high-purity Shao alloy can be covered with a cohesive film which is cold-permeable, but cannot pass through such a film, for example, including alumina or aluminum nitride. (The full text of the theme of the Awakening Awakening is incorporated here by bow. .. A '· -... 10
Bercaw等人之美國專利第5,811，195號，核發日期Μ% 年9月22日，名稱「半導體處理設備用之防蝕性鋁物件」， 進一步揭示結物件之量可占鋁物件之約〇1%至約6〇% 15 重量比。但用於高於約250。(：之物件操作溫度，鋁物件之 鎂含量係占鋁物件之約〇.1%重量比至約15%重量比。此外 說明-種物件，其中於特定例，鎂以外之雜質可高達約 2.0%重置比。其中一範例為有薄膜覆蓋於物件本體外部， 此處薄膜包含氧化鋁或鋁。另一例為厚度至少約〇〇〇25微 米之鹵化鎮m於！呂物件外表面±。該專利案揭示之主 題以引用方式併入此處。 20 對可用於製造半導體加工設備之紹合金，該合金不僅 必須含低濃度雜質原子，同時也須具有滿意的機械性質。 機械性質必須可機製而提供具有所需尺寸之物件。例如若 合金太過柔軟，則難以鑽孔，原因在於合金材料於鑽孔期 間容易變沾黏而非被鑽頭所去除。機製物件尺寸的控制更 8 1223354 玖、發明說明 為困難。造成機製成本的增高。物件的機製性質也影響物 件於真空表現能力。例如處理室必須具有足夠結構剛性以 及幵v支耐!生，才此相對於高度真空作適當密封。最後當物 件接受處理（例如為了降低應力接受處理）時，處理必須確 5保負載與應力係均勾一致的移轉。 金屬手冊」，第九版，第2期，版權年，美國金 屬學會出版，描述紹合金之加熱處理，始於第以頁。特別 對可熱處理紹合金以及非可熱處理紹合金而言，退火走徐 冷加工期間形成的應力，可藉於約灣(用於批次處理)至 1〇約45〇°C(用於連續處理）溫度範圍加熱達成。 通常應用於紹合金之「加熱處理」一詞限於用來提高 沉殿可硬化之锻造及鑄造合金的強度及硬度。此種合金稱 作可熱處理」合金，俾與藉加熱以及處理無法顯著加強 的合金區別。後者合金通稱為「非可熱處理」合金，非可 15熱處理合金於锻造形式時主要係靠冷加工來提高強度。厂 盃屬手冊」第29頁，表1提供若干常見锻造紹合金之典型 完整退火處理。5XXX系列鋁合金用於製造半導體加工裝置 特別令人感興趣，原因在於此種系列之若干合金提供於可 接又之中等範圍之雜質濃度，同時提供足夠鎂含量俾於 2〇 Bercaw等人之專利案所述之方式發揮效用。 當鋁合金製造的物件用於腐蝕性氣氛時，經常需要保 護性塗層（如陽極化層）於鋁表面上，對鋁用於半導體加工 時特別為真，半導體加工採用含腐純氯或敦之姓刻劑氣 體以及由此等氣體產生的電漿。特殊鋁合金表面之穩定陽 9 1223354 玖、發明說明 極化層可輔助於或接近鋁合金表面維持自化物保護成分。 陽極化層也有助於防止鋁表面以及任何其它存在於鋁表面 之保護層的磨蝕。陽極化層於覆於特用鋁合金上方之鹵化 物保護元件之組合，提供於腐蝕環境可長期發揮功能的物 件。保護性陽極化膜劣化，不僅造成設備維護上之重大花 費以及t置更換成本，同時例如若感受器出現顯著表面 缺陷’則此等缺陷可能轉移影響感受器頂上的石夕晶圓，於 晶圓形成污染’結果導致裝置漏電流或甚至短路。如此可 能影響裝置的可靠度。不可靠的產品將嚴重毀損製造商信 10 譽 15 20 鋁合金6061為典型用於製造半導體加工設備之標準鋁 合金。6〇6丨合金通常具有下列雜質含量，以重量百分比表 示：鎂濃度約0_8%至約L2%，矽濃度由〇 4%至約〇.8%， 鐵濃度至多0.7%’銅濃度由約。15%至約〇 4%，鈦濃度至 多〇趟，猛濃度約〇.15%，鋅濃度約〇25%，絡濃度於約 0.04%至約G.35% ’其它雜質各自不超過於約Q㈣，其它 雜貝總里不超過約〇. 15 %。 其中部分元素對處理室内製造的半導體元件有害，包 括606〗合金。例如用作為半導體電路之金屬互連裝置之銅 層由於電阻低故為所需。但半導體處理室内元件存在有銅 雜質則不合所需’原因在於處理室内處理的基板上存在有 來自處理室元件之銅污染’將影響存在於基板上之積體電 路元件性能。 已經發展出若干特⑽合金供半導體加工設備使用， 10 1223354 玖、發明說明 但此等合金製造上特別昂貴。 =望有一種鋁合金其具有製造上之成本效益，具有所 需^械^波^匕學)性質，其組合陽極化塗層之效果良好，可提 供加工裝置之長期工作壽命。 5 【明内】 發明概要 發明人發現於链合金表面及内部形成「微_狀包蹲體， 於物件表面藉陽極化塗覆保護時可能干擾物件性能。發明 人也發現經由控制存在於合金本身之特定雜質濃度，可將 10此種避fc获包鱼暴之生成控制至相當程度。 特別，發明人測定具有下述雜質（存在量以重量百分 比表示）之鋁合金雖然製造上相對價廉，但當用於製造半 導體加工裝置時性能良好：矽濃度於約0 4%至約0·8%之範 圍’銅濃度於約0.1 5%至約0.30%之範圍，鐵濃度於約 15 〇·〇01%至約0·20%之範圍，錳濃度於約0.001%至約〇.14% 之範圍’鋅濃度於約〇·〇〇1%至約0·15%之範圍，鉻濃度於 約0.04%至約0.28%之範圍，鈦濃度於約0 001〇/〇至約0 06〇/〇 之範圍，以及鎂濃度於約0.8%至約1.2%之範圍。存在於銘 合金之其它雜質總量不超過0.15%，各別其它雜質限於最 20 大量各自為0.05%。 铭合金除了化學組成要求外，也要求鋁合金就來自於 合金中存在的雜質形成的微粒而言，符合特定規格。雜質 化合物之懲粒狀聚結體争，至少8 5 %全部粒子之大小需小 欲5微米。低於15%之粒子之大小於5微米至2〇微米之範圍 11 1223354 玖、發明說明 。大於20微#大小之粒子不超過1%，且無任何粒子大於 40微米。 鋁物件被擠塑成為預定形狀後，或鋁物件由坯塊或坯 段被機製成為預定形狀後，典型應力係於約4丨5或以下 5之溫度解除。應力解除可提供更穩定的表面，供施用陽極 化保護膜，以及提供改良之機械效能性質。 圖式簡單說明 結合附圖考慮後文詳細說明時，將對本發明獲得更佳 了解，附圖中： 10 帛1圖顯示用於半導體基板製造方法之習知反應器室 100之示意圖。 第2圖為結構200之示意頂視圖，結構2〇〇於有缺陷2〇8 之陽極化塗覆層204下方包含鋁合金（圖中未顯示）。 第3A圖為顯微相片之示意圖，其顯示導致第2圖之陽 15極化塗覆層204上表面209所示缺陷208之結構亦即鋁合金 302及陽極化塗覆層304之剖面圖。 第3B圖為顯微相片，其顯示本發明之鋁合金322之剖 面圖，此處於陽極化塗覆層324上表面329未觀察得任何缺 陷。 20 【實施方式】 較佳實施例之詳細說明 於詳細說明之前，須注意本說明書及隨附之申請專利 範圍使用單數形「-」&「該」除非於内文有其它明白指 示，否則單數形也包括複數形。 12 1223354 玖、發明說明 本發明也提供一種對腐蝕性處理條件有抗性之半導體 處理裝置。第1圖顯示習知用於半導體基板製造方法，例 如化學氣相沉積（c V D)或蝕刻之習知反應器室1 〇 〇之示意圖 。此種半導體基板製造方法典型讓反應器室内部各元件置 5於腐蝕性含！i素物種118之下。腐蝕性特高之氣體為典型 用於電浆清潔反應器室元件之氣體混合物，例如四氣化碳 與氧化亞氮（CFVI^O)以及四氟乙烯與氧（cjjo〗）之氣體 混合物（舉例說明但非限制性）。半導體處理過程中，於週 期性之反應器室清潔期間，反應器室元件係接觸1〇〇它至 10 450 C之高溫以及接觸腐蝕性含鹵素氣體混合物。 參妝第1圖，某些反應器室元件例如孔板丨丨〇(用來輸 送處理氣體至反應器室，且作為激發電漿之射頻電極）以 及感受器m(承載半導體基板114，也作為射頻電極）習知 係由銘製成，帶有藉陽極化塗層保護之表面。 15 半導體加工設備中最常用的鋁合金為6061合金。為了 瓖鋁合金對抗腐蝕，陽極化保護層施用於鋁合金之將暴露 於腐蝕性加工環境之表面上。為了獲得加工裝置之最佳防 蝕性以及最長可接受之工作壽命，物件係以特殊方式製造 。為了獲得最佳結果’用於物件本體之銘合金須由特殊潔 20 淨紹合金製成。 、 第2圖顯示半導體加工裳置元件之示意頂視圖，該加 工裝置元件係由經由陽極化塗覆層2〇4保護之6〇61鋁合金（ 圖中未顯示）製造。裝置元件暴露於電㈣刻環境後， 缺陷208出現於陽極化塗覆層2〇4表面2〇9上。隨著時間的 13 1223354 玖、發明說明 經過缺陷208變足夠嚴重，於存在有缺陷2〇8區域212，污 染物微粒開始片落。 第3A圖顯示半導體加工室壁（圖中未顯示）之一區段 300之示思剖面圖，此處室壁包括6061紹合金3〇2，帶有保 5護性陽極化層於鋁合金302之上表面305上，其形成鋁 口金302與陽極化層304間之界面307。典型地，此種陽極 化層304厚度係於約〇·3密耳（8微米）至約4〇密耳（1〇〇微米） 之範圍。發明人發現於加工室區段3〇〇上表面3〇9之缺陷 3 11的起因係存在於6〇6丨鋁合金之雜質及雜質化合物形成 1〇聚結體308。聚結體308形成導管或通道31〇，導管或通道 延伸貫穿6061鋁合金本體303各部分，且延伸入陽極化塗 覆層304 ’而於陽極化塗覆層3〇4上表面3〇9產生缺陷3u。 結果例如腐蝕性電漿物種可穿過通道3 1〇向下穿過陽極化 塗覆層304，攻擊存在於陽極化塗覆層3〇4與本體3〇3間之 15界面307的1呂。第3A圖所示機轉說明於陽極化6061鋁加工 至上表面觀察得的缺陷208成因，如第2圖所示。 重要地須敘述「裸」6061合金暴露於空氣時形成厚度 、’、勺30埃至約5〇埃之天然氧化物，天然氧化物形成時，鋁合 金上表面之雜質聚結體於天然氧化物造成問題，該問題類 2〇似陽極化層之問題甚至更惡化。存在有此種聚結體大為降 低天然氧化物所能提供的保護。 鐵是一項問題金屬，鐵存在於半導體加工設備使用的 鋁合金時造成腐蝕。鋁合金製造過程中，含鐵化合物大型 ♦、、Ό體經#於合金内部形成。第3A圖所示大量聚結體3〇8 14 1223354 玖、發明說明 包括鐵或含鐵化合物，其係存在於鋁合金之各個不同位置 。含鐵聚結體可能出現於合金片材、述段、或擠塑部分内 斗及表面上。用於半導體業以外之產業應用，聚結體不會 造成問題。但詩半導體加讀備，用於製造加王容器（或 八匕加工至内部裝置）的起始物料存在有含鐵聚結體可能引 發重大問題。於本體303與保護性陽極化塗覆層3〇4間之界 面307，存在有包括含鐵化合物之聚結體3〇8，促成形成隧 道310，隧道310貫穿陽極化塗覆層3〇4至本體3〇3之基底鋁 。隧道3H)將基底轉露於各種處理化學品，其可能腐触 10合金本體303。此點對於銘應用於半導體加工裝置時特別為 真，半導體加工裝置中採用腐飯性含氣或含氣餘刻劑氣體 以及由此等氣體生成的電漿。最終若腐蝕夠嚴重，則裝置 表面全部面積片落入半導體加工室内，污染隨後於該加工 至内進行的加工處理操作。雖然鐵本身不會對合金提供任 15何重大有利品質，但由合金去除鐵造成合金製造成本的增 高。隨著鐵含量的增加，鋁合金的製造成本提高。 如前文說明有關半導體加工裝置，若使用鋁合金於半導 體加工應用，則需控制呈元素形式及化合物形式之特殊雜質 。發明人發現就聚結體形成方面而言，特別須考慮之元素包 2〇括矽、鐵及銅。也有其它雜質必須控制於特殊範圍。 為了防止形成第3A圖所示之通道及微通道31〇，以及 形成微裂縫，微裂缝可能導致含鋁半導體加工設備元件的 污染及腐蝕，發明人發展出一種「潔淨」鋁合金。潔淨合 金係設計成減少第3A圖所示雜質化合物聚結體3〇8數目及 15 1223354 玖、發明說明 大小’同時將合金成本維持於儘可能低成本。 潔淨铭合金組成係小心控制，讓存在於合金之雜質落 入下述濃度範圍。存在於合金之雜質限於下述重量百分比 範圍·矽濃度於約0.4%至約〇·8〇/0之範圍；銅濃度於約 5 〇·15%至約0.3%之範圍（更典型約〇15%至約〇·25%);鐵濃 度於約0.001 %至約0.2%之範圍（更典型高達〇1%);錳濃度 10 於約0.001%至約0.14%之範圍，鋅濃度於約〇〇〇1%至約 0.15%之範圍，鉻濃度於約〇〇4%至約〇·28%之範圍，鈦濃 度於約0顧％至約0.06%之範圍，以及鎮濃度於約〇8%至 約1.2%之範圍。存在於鋁合金之其它雜質總量不超過 0.15%，各別其它雜質限於最大量各自為〇〇5%。 15 與其它雜質獨立無關，#明人發現較為有害的雜質為 鐵石夕及銅。發明人進一步確定石夕含量須維持於原子濃度 低於約0.8%重量比，鐵須維持於原子濃度約Q_QQi%· 〇·2%重量比，以及銅須維持於原子濃度約〇15%至約〇·3% 重量比。典型地，低於約〇·1%重量比之鐵濃度以及於約 〇·15%至約〇·25%重量比範圍之銅漢度可獲得良好效果。 此外办/爭銘合金之雜質微粒大小及分佈係控制於特 定範圍。雜質微粒係於特定限度範圍内，故至少85%全部 2〇粒子尺寸係小於5微米。5微米至2〇微米尺寸之粒子低於 15〇/。。大於20微米粒子不超賴，且無任何大⑽微米之 粒子。 分析技術係基於於掃 影像分析。放大倍率 用於測定粒子大小及大小分佈之 描電子顯微鏡（SEM)下方之反向散射 16 1223354 玖、發明說明 500乜俾汴比組成粒子。各個影像面積約為微米微 米。數位解析度至少〇·2微米/像素。由直徑〇75吋之樣本 區至少隨機拍攝40張影像，俾獲得金屬顯微結構各區的良 好評比，確定有意義的統計分析。反向散射影像以數位方 5式儲存供隨後作統計分析之用。影像傳輸至影像分析儀， 偵測與測定平均原子數大於鋁（影像中的白色部分）之粒子 分佈。數位解析度允許測定小至〇·2微米的粒子。測定粒 徑分佈用之參數為：面積直徑等於圓形ρ=2χ(Α/π)平方根 ’此處Α為粒子面積。類別限制如後：0.2 ; 1 ; 2 ; 3 ; 4 ; 10 5 ; 20 ; 40。各類粒子數目經過測定然後對欲測量粒子總 數規度化至100%。 第3B圖顯示半導體處理室壁（圖中未顯示）之一區段 320之示意剖面圖，此處該室壁包括帶有陽極化保護塗覆 層324之本發明合金322，塗覆層形成與鋁合金本體323之 15界面327。典型地，此種陽極化塗覆層324之厚度係於約 〇·3密耳（8微米）至約4·〇密耳（1〇〇微米）之範圍。雜質化合物 聚結體328仍然存在於鋁合金322本體323，但聚結體328的 平均尺寸遠較小，且不會產生貫穿至陽極化塗覆層324上 表面329的通道。如此可實質延長半導體加工室壽命。 !〇 當無陽極化保護性塗覆層施用於鋁表面時，唯一保護 層為厚度約30埃至約50埃之天然氧化物，天然氧化物係於 鋁暴露於空氣時，於鋁表面上形成，使用符合此處揭示之 微粒要求及雜質含量濃度的鋁合金可改良天然氧化物之保 護能力。 17 1223354 玖、發明說明 别文揭示之具體實施例絕非意圖囿限本發明之範圍， …、叫技藝人士鑑於本揭示内容可將此等具體實施例擴充而 對應後文申請專利之本發明主旨。 【固式簡單說明】 結合附圖考慮後文詳細說明時，將對本發明獲得更佳 了解，附圖中： 第1圖顯示用於半導體基板製造方法之習知反應器室 100之示意圖。 第2圖為結構200之示意頂視圖，結構200於有缺陷2〇8 10之陽極化塗覆層204下方包含鋁合金（圖中未顯示 第3 A圖為顯微相片之示意圖，其顯示導致第2圖之陽 極化塗覆層204上表面209所示缺陷208之結構亦即鋁合金 302及陽極化塗覆層304之剖面圖。 第3B圖為顯微相片，其顯示本發明之|呂合金322之叫 15 面圖’此處於陽極化塗覆層3 24上表面329未觀察得任何缺 陷。 【圖式之主要元件代表符號表】 100···反應器室 208、311…缺陷 110···孔板 209…表面 212…區域 300、320···區段 302···銘合金 303···本體 112···感受器 114…基板 118···含鹵素物種 200···半導體加工裝置元件 204···陽極化塗覆層 304…保護性陽極化層 18 1223354 玖、 305 307， 308 310· 發明說明 309、329···上表面 327···界面 328···聚結體 •通道 322···本發明合金 323···鋁合金本體 324···陽極化保護性塗覆層 19Bercaw et al. U.S. Patent No. 5,811,195 issued on September 22, 2009 under the name "corrosion-resistant aluminum articles for semiconductor processing equipment" further reveals that the amount of knotted articles can account for approximately 0.001% of aluminum articles To about 60% 15 by weight. But used above about 250. (: The operating temperature of the object, the magnesium content of the aluminum object is about 0.1% by weight to about 15% by weight of the aluminum object. In addition, a kind of object, of which, in specific examples, impurities other than magnesium can be as high as about 2.0 % Reset ratio. One example is a film covering the outside of the body of the object, where the film contains alumina or aluminum. The other example is a halogenated town with a thickness of at least about 00525 μm on the outer surface of the object ±. This The subject matter disclosed in the patent case is incorporated herein by reference. 20 For alloys that can be used to make semiconductor processing equipment, the alloy must not only contain low concentrations of impurity atoms, but also have satisfactory mechanical properties. Mechanical properties must Provide objects with the required size. For example, if the alloy is too soft, it is difficult to drill, because the alloy material tends to stick during the drilling instead of being removed by the drill. Control of the size of the mechanical object 8 1223354 玖, invention The explanation is difficult. It causes the mechanism cost to increase. The mechanical properties of the object also affect the ability of the object to express in vacuum. For example, the processing room must have sufficient structural rigidity to幵 v is resistant, so it is properly sealed relative to a high vacuum. Finally, when the object is processed (for example, to reduce stress), the processing must ensure that the load and stress are transferred in the same way. Metal Manual ", Ninth Edition, Issue 2, Copyright Year, published by the American Society of Metals, describing the heat treatment of Shao alloys, beginning on page 1. Especially for heat-treatable Shao alloys and non-heat-treatable Shao alloys, annealing and cold working are performed. The stress formed during this period can be achieved by heating in the temperature range of about Wan (for batch processing) to 10 about 45 ° C (for continuous processing). The term "heat treatment" usually applied to Shao alloy is limited to use To increase the strength and hardness of Shendian's hardenable forged and cast alloys. Such alloys are called heat-treatable "alloys and are different from alloys that cannot be significantly strengthened by heating and processing. The latter alloys are commonly known as" non-heat-treatable "alloys. Non-15 heat treatable alloys are mainly formed by cold working in the form of forging to increase strength. The factory cup manual is on page 29. Table 1 provides some typical forging alloys. Completely annealed. 5XXX series aluminum alloys are particularly interesting for the manufacture of semiconductor processing devices, because some alloys of this series provide impurity concentrations in accessible and moderate ranges, while providing sufficient magnesium content to be less than 20 Bercaw The method described in the patents of the others works effectively. When articles made of aluminum alloys are used in corrosive atmospheres, protective coatings (such as anodized layers) are often required on aluminum surfaces. This is especially true when aluminum is used in semiconductor processing. For truth, semiconductor processing uses rotten pure chlorine or Dun's engraving gas and plasma generated from these gases. Stability of the surface of special aluminum alloy 9 1223354 发明, invention description Polarization layer can assist or approach the surface of aluminum alloy Maintains self-protective components. The anodized layer also helps prevent abrasion of the aluminum surface and any other protective layers present on the aluminum surface. The combination of the anodizing layer and the halide protection element over the special aluminum alloy provides a long-term function in a corrosive environment. Deterioration of the protective anodizing film not only causes significant expenses for equipment maintenance and replacement cost, but also, for example, if there are significant surface defects on the susceptor, these defects may transfer and affect the Shixi wafer on the top of the susceptor, which will cause contamination on the wafer. 'As a result, device leakage or even short circuit occurs. This may affect the reliability of the device. Unreliable products will severely damage the manufacturer's letter. 10 Reputation 15 20 Aluminum alloy 6061 is a standard aluminum alloy typically used in the manufacture of semiconductor processing equipment. The 606 alloy generally has the following impurity content, expressed in weight percent: a magnesium concentration of about 0-8% to about L2%, a silicon concentration of 0.4% to about 0.8%, an iron concentration of up to 0.7%, and a copper concentration of about. 15% to about 04%, titanium concentration at most 0 times, fierce concentration of about 0.15%, zinc concentration of about 025%, complex concentration of about 0.04% to about G.35% 'Other impurities each do not exceed about Q㈣ , The total miscellaneous miscellaneous shellfish does not exceed about 0.15%. Some of these elements are harmful to semiconductor components manufactured in the processing chamber, including 606 alloys. For example, a copper layer used as a metal interconnection device for a semiconductor circuit is required because of its low resistance. However, the presence of copper impurities in the components of the semiconductor processing chamber is not desirable because the presence of copper contamination from the processing chamber components on the substrate processed in the processing chamber will affect the performance of the integrated circuit components present on the substrate. Several special rhenium alloys have been developed for use in semiconductor processing equipment. 10 1223354 rhenium, invention description But these alloys are particularly expensive to manufacture. = There is an aluminum alloy that is cost-effective in manufacturing and has the required properties. Its combined anodized coating has a good effect and can provide long-term working life of the processing device. 5 [Mei Nai] Summary of the invention The inventor found that a "micro-shaped bag squatting body" was formed on the surface and inside of the chain alloy, which may interfere with the performance of the object when protected by anodizing coating on the surface of the object. The inventor also found that the existence of the alloy was controlled The specific impurity concentration can control the generation of such fc-captured fishstorms to a considerable degree. In particular, the inventors determined that aluminum alloys with the following impurities (the amount of which is expressed by weight percentage) are relatively inexpensive to manufacture, But when used in the manufacture of semiconductor processing devices, the performance is good: the silicon concentration is in the range of about 0.4% to about 0.8%; the copper concentration is in the range of about 0.15% to about 0.30%; and the iron concentration is about 15%. A range of 01% to about 0.20%, a manganese concentration in a range of about 0.001% to about 0.14%, a zinc concentration in a range of about 0.0001% to about 0.15%, and a chromium concentration in a range of about 0.04 % To about 0.28%, titanium concentration in a range of about 0.001 to about 0 06 //, and magnesium concentration in a range of about 0.8% to about 1.2%. The total amount of other impurities present in Ming alloy Not more than 0.15%, and each other impurity is limited to a maximum of 20 and each is 0.05%. In addition to chemical composition requirements, aluminum alloys are also required to meet specific specifications with respect to particles formed from impurities present in the alloy. Impurity compounds are considered to be granular agglomerates, and at least 85% of the total particle size needs to be small 5 microns. The size of particles below 15% is in the range of 5 microns to 20 microns. 11 1223354 玖, description of the invention. The size of particles larger than 20 microns # does not exceed 1%, and no particles are larger than 40 microns. After extrusion into a predetermined shape, or after an aluminum object is formed into a predetermined shape from a block or billet, the typical stress is relieved at a temperature of about 4 5 or below 5. Stress release can provide a more stable surface for anode application Protective film, and provide improved mechanical performance properties. The drawings are briefly explained in conjunction with the accompanying drawings, which will give a better understanding of the present invention. In the drawings: 10 帛 1 shows a method for manufacturing a semiconductor substrate A schematic diagram of a conventional reactor chamber 100 is shown in Fig. 2. Fig. 2 is a schematic top view of a structure 200. The structure 200 contains an aluminum alloy under the defective anodized coating 204 of the 208 (in the figure). (Not shown). Figure 3A is a schematic view of a photomicrograph showing the structure that causes the defects 208 shown on the upper surface 209 of the polarized coating layer 204 of Figure 15 of Figure 2 namely the aluminum alloy 302 and the anodized coating layer 304. Fig. 3B is a photomicrograph showing a cross-sectional view of the aluminum alloy 322 of the present invention, where no defect is observed on the upper surface 329 of the anodized coating layer 324. 20 [Embodiments] Preferred Examples Detailed description Before detailed description, please note that the use of the singular form "-" & "the" in this specification and the accompanying patent application scope includes the singular form, as well as the plural form, unless otherwise clearly indicated in the text. 12 1223354 (ii) Description of the invention The present invention also provides a semiconductor processing apparatus that is resistant to corrosive processing conditions. FIG. 1 shows a schematic diagram of a conventional reactor chamber 100, which is conventionally used in semiconductor substrate manufacturing methods, such as chemical vapor deposition (c V D) or etching. This type of semiconductor substrate manufacturing method typically places the components inside the reactor chamber 5 in a corrosive atmosphere! i prime species under 118. Extremely corrosive gases are gas mixtures typically used for plasma cleaning of reactor chamber components, such as gas mixtures of carbon tetrachloride and nitrous oxide (CFVI ^ O) and tetrafluoroethylene and oxygen (cjjo) (for example Illustrative but non-limiting). During semiconductor processing, during periodic reactor chamber cleaning, the reactor chamber elements are exposed to temperatures as high as 1000 to 10 450 C and to corrosive halogen-containing gas mixtures. See Figure 1. Some reactor chamber components such as orifice plates (used to deliver processing gas to the reactor chamber and act as RF electrodes for exciting plasma) and sensors m (bearing semiconductor substrate 114, also used as radio frequency) (Electrode) is made from inscriptions with a surface protected by an anodized coating. 15 The most commonly used aluminum alloy in semiconductor processing equipment is 6061 alloy. To protect the aluminum alloy against corrosion, an anodized protective layer is applied to the surface of the aluminum alloy that will be exposed to a corrosive processing environment. In order to obtain the best corrosion resistance of the processing equipment and the longest acceptable working life, the articles are manufactured in a special way. For best results, the alloy used in the body of the object must be made of a special clean alloy. Figure 2 shows a schematic top view of a semiconductor processing device, which is manufactured from a 6061 aluminum alloy (not shown) protected by anodized coating 204. After the device element is exposed to the electrical engraving environment, a defect 208 appears on the surface 204 of the anodized coating layer 204. With the time of 13 1223354, the description of the invention, the defect 208 becomes severe enough, and in the presence of the defective 208 area 212, the pollutant particles start to fall off. Figure 3A shows a cross-sectional view of a section 300 of a semiconductor processing chamber wall (not shown). Here, the chamber wall includes 6061 alloy 302, with a protective anodized layer on aluminum alloy 302. On the upper surface 305, it forms an interface 307 between the aluminum gold 302 and the anodized layer 304. Typically, the thickness of such an anodized layer 304 ranges from about 0.3 mils (8 microns) to about 40 mils (100 microns). The inventors found that the defect 3009 on the upper surface of the processing chamber section 3009 was caused by impurities and impurity compounds existing in the 6006 aluminum alloy to form 10 agglomerates 308. The agglomerate 308 forms a duct or channel 31. The duct or channel extends through each part of the 6061 aluminum alloy body 303, and extends into the anodized coating layer 304 ', and is generated on the anodized coating layer 304 upper surface 309. Defect 3u. As a result, for example, the corrosive plasma species can pass through the channel 3 10 and pass through the anodized coating layer 304, attacking the 1 lu at the 15 interface 307 between the anodized coating layer 30 and the body 30. The mechanism shown in FIG. 3A illustrates the cause of defect 208 observed on the anodized 6061 aluminum processed to the upper surface, as shown in FIG. 2. It is important to describe the thickness of the "naked" 6061 alloy when exposed to air. The natural oxides of 30 Angstroms to about 50 Angstroms are formed. When natural oxides are formed, impurities on the upper surface of the aluminum alloy agglomerate to the natural oxides. This causes problems, and the problems of the 20-like anodized layer are even worse. The presence of such agglomerates greatly reduces the protection that natural oxides can provide. Iron is a problem metal, and it causes corrosion when it is present in aluminum alloys used in semiconductor processing equipment. During the aluminum alloy manufacturing process, large iron-containing compounds are formed inside the alloy. A large number of agglomerates 3008 14 1223354 shown in Figure 3A 玖 Description of the invention Including iron or iron-containing compounds, which are present in various positions of the aluminum alloy. Iron-containing agglomerates may appear on the inner buckets and surfaces of alloy sheets, segments, or extruded parts. For industrial applications outside the semiconductor industry, agglomerates do not cause problems. However, Poetry Semiconductor added that the presence of iron-containing agglomerates in the starting materials used to manufacture King Containers (or eight daggers processed into internal devices) may cause major problems. At the interface 307 between the body 303 and the protective anodized coating layer 304, there is an agglomerate 308 including an iron-containing compound, which promotes the formation of a tunnel 310, and the tunnel 310 penetrates the anodized coating layer 304 to Base aluminum of body 303. Tunnel 3H) The substrate is exposed to various processing chemicals, which may corrode the 10 alloy body 303. This is especially true when Ming is applied to semiconductor processing equipment. The semiconductor processing equipment uses a rotten gas or a gas-containing residual agent gas and a plasma generated from such a gas. In the end, if the corrosion is severe enough, the entire area of the device surface will fall into the semiconductor processing chamber, contaminating the subsequent processing operations performed within that processing. Although iron itself does not provide any significant beneficial quality to the alloy, the removal of iron from the alloy causes an increase in the manufacturing cost of the alloy. As the iron content increases, the manufacturing cost of aluminum alloys increases. As explained in the previous section about semiconductor processing equipment, if aluminum alloys are used for semiconductor processing applications, special impurities in the form of elements and compounds need to be controlled. The inventors have found that in terms of agglomerate formation, elements that must be considered particularly include silicon, iron, and copper. There are also other impurities which must be controlled in a special range. In order to prevent the formation of the channels and micro-channels 31 shown in Figure 3A, and the formation of micro-cracks, micro-cracks may cause contamination and corrosion of aluminum-containing semiconductor processing equipment components. The inventors developed a "clean" aluminum alloy. The clean alloy system is designed to reduce the number of impurity compound agglomerates 3008 shown in Figure 3A and 15 1223354 发明, description of the invention, and the size of the alloy while keeping the cost of the alloy as low as possible. The composition of the clean alloy is carefully controlled so that impurities present in the alloy fall within the concentration range described below. Impurities present in the alloy are limited to the following weight percent ranges: silicon concentration in the range of about 0.4% to about 0.80 / 0; copper concentration in the range of about 50.15% to about 0.3% (more typically about 0.15 % To about 0.25%); iron concentration in the range of about 0.001% to about 0.2% (more typically up to 0.001%); manganese concentration 10 in the range of about 0.001% to about 0.14%, and zinc concentration in the range of about 0.00%. 0.001% to about 0.15%, chromium concentration in the range of about 0.004% to about 0.28%, titanium concentration in the range of about 0% to about 0.06%, and town concentration in the range of about 0.8% to A range of about 1.2%. The total amount of other impurities in the aluminum alloy does not exceed 0.15%, and the maximum amount of each other impurity is limited to 0.05% each. 15 Independent of other impurities, # Mingren found that the more harmful impurities are iron stone and copper. The inventors further determined that the content of Shi Xi must be maintained at an atomic concentration of less than about 0.8% by weight, iron must be maintained at an atomic concentration of about Q_QQi% ··· 2% by weight, and copper must be maintained at an atomic concentration of about 0.15% to about 0.3% by weight. Typically, good results are obtained with iron concentrations below about 0.1% by weight and copper manganese in the range of about 0.15% to about 0.25% by weight. In addition, the size and distribution of the impurity particles in the alloy should be controlled within a specific range. Impurity particles are within a certain limit, so at least 85% of all 20 particle sizes are smaller than 5 microns. Particles with a size of 5 to 20 microns are less than 150%. . Particles larger than 20 microns are not overwhelming, and there are no particles larger than 20 microns. The analysis technique is based on scanning image analysis. Magnification Backscattering under the SEM for measuring particle size and size distribution 16 1223354 玖, description of invention 500 乜 俾 汴 ratio particles. The area of each image is about micrometers. Digital resolution of at least 0.2 micron / pixel. At least 40 images were randomly taken from a sample area with a diameter of 075 inches, and the favorable reviews of each area of the metal microstructure were obtained to determine a meaningful statistical analysis. Backscattered images are stored digitally in a format of 5 for subsequent statistical analysis. The image is transmitted to an image analyzer to detect and measure the distribution of particles with an average atomic number greater than aluminum (the white part in the image). Digital resolution allows the measurement of particles as small as 0.2 microns. The parameter used to determine the particle diameter distribution is: the area diameter is equal to the square ρ = 2χ (Α / π) square root 'where A is the particle area. The category restrictions are as follows: 0.2; 1; 2; 3; 4; 10 5; 20; 40. The number of each type of particle is measured and then the total number of particles to be measured is normalized to 100%. FIG. 3B shows a schematic cross-sectional view of a section 320 of a semiconductor processing chamber wall (not shown). Here, the chamber wall includes an alloy 322 of the present invention with an anodized protective coating 324. 15 surface 327 of the aluminum alloy body 323. Typically, the thickness of such anodized coating layer 324 ranges from about 0.3 mils (8 microns) to about 4.0 mils (100 microns). Impurity compound agglomerates 328 still exist in the aluminum alloy 322 body 323, but the average size of the agglomerates 328 is much smaller, and no channels are formed that penetrate the upper surface 329 of the anodized coating layer 324. This can substantially extend the life of the semiconductor processing room. When a non-anodized protective coating is applied to the aluminum surface, the only protective layer is a natural oxide with a thickness of about 30 angstroms to about 50 angstroms. The natural oxide is formed on the aluminum surface when the aluminum is exposed to air. The use of aluminum alloys that meet the particulate requirements and impurity content concentrations disclosed herein can improve the protective ability of natural oxides. 17 1223354 玖 The specific embodiments disclosed in the description of the invention are by no means intended to limit the scope of the invention, ......, in view of the content of the disclosure, these specific embodiments can be expanded to correspond to the subject matter of the invention for which patents are applied later . [Solid type simple explanation] The present invention will be better understood when considering the detailed description below with reference to the accompanying drawings. In the drawings: FIG. 1 shows a schematic diagram of a conventional reactor chamber 100 used for a semiconductor substrate manufacturing method. Figure 2 is a schematic top view of the structure 200. The structure 200 contains an aluminum alloy under the anodized coating layer 204 of the defective 2080 (Figure 3A is not shown in the figure is a schematic photomicrograph, which shows the The structure of the defect 208 shown on the upper surface 209 of the anodized coating layer 204 in Fig. 2 is a cross-sectional view of the aluminum alloy 302 and the anodized coating layer 304. Fig. 3B is a micrograph showing the invention | The surface 15 of alloy 322 is called 'here, no defect is observed on the upper surface 329 of the anodized coating layer 3 24. [Key components of the figure represent the symbol table] 100 ··· Reactor chamber 208,311 ... Defect 110 · Orifice 209 ... Surface 212 ... Area 300, 320 ... Segment 302 ... Ming Alloy 303 ... Body 112 ... Sensor 114 ... Substrate 118 ... Halogen-containing species 200 ... Semiconductor processing Device element 204 ... Anodized coating layer 304 ... Protective anodized layer 18 1223354 玖, 305 307, 308 310. Description of the invention 309, 329 ... Upper surface 327 ... Interface 328 ... Agglomerates • Channel 322 ... The alloy 323 of the present invention ... Aluminum alloy body 324 ... Anodized protective coating Overlay 19